Synthesis of liquid fuels and chemicals from oxygenated hydrocarbons

ABSTRACT

Described are methods for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons in a single reactor. The method includes reacting a water soluble oxygenated hydrocarbon in the presence of a catalyst at a temperature, pressure, and weight hour space velocity for a time sufficient to produce a self-separating, three-phase product stream comprising a vapor phase, an organic phase, and an aqueous phase. A portion of the organic phase can be reacted to produce alkanes, alkenes, alcohols, and aromatics.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of pending U.S. application Ser. No.13/171,715, filed Jun. 29, 2011 now U.S. Pat. No. 8,367,882 and Ser. No.13/163,439, filed Jun. 17, 2011 now U.S. Pat. No. 8,362,307, which arecontinuations of U.S. application Ser. No. 12/044,876, filed Mar. 7,2008 now U.S. Pat. No. 8,017,818, which claims the benefit of USProvisional App. Nos. 60/985,475, filed Nov. 5, 2007, 60/985,500, filedNov. 5, 2007, and 60/905,703, filed Mar. 8, 2007. All of theseapplications are incorporated by reference herein in their entirety.

BACKGROUND

Significant amount of attention has been placed on developing newtechnologies for providing energy from resources other than fossilfuels. Biomass is a resource that shows promise as a fossil fuelalternative. As opposed to fossil fuel, biomass is also renewable.

One type of biomass is plant biomass. Plant biomass is the most abundantsource of carbohydrate in the world due to the lignocellulosic materialscomposing the cell walls in higher plants. Plant cell walls are dividedinto two sections, primary cell walls and secondary cell walls. Theprimary cell wall provides structure for expanding cells and is composedof three major polysaccharides (cellulose, pectin, and hemicellulose)and one group of glycoproteins. The secondary cell wall, which isproduced after the cell has finished growing, also containspolysaccharides and is strengthened through polymeric lignin covalentlycross-linked to hemicellulose. Hemicellulose and pectin are typicallyfound in abundance, but cellulose is the predominant polysaccharide andthe most abundant source of carbohydrates.

Most transportation vehicles, whether boats, trains, planes andautomobiles, require high power density provided by internal combustionand/or propulsion engines. These engines require clean burning fuelswhich are generally in liquid form or, to a lesser extent, compressedgases. Liquid fuels are more portable due to their high energy densityand their ability to be pumped, which makes handling easier. This is whymost fuels are liquids.

Currently, biomass provides the only renewable alternative for liquidtransportation fuel. Unlike nuclear and wind applications, and for themost part solar resources, biomass is capable of being converted into aliquid form. Unfortunately, the progress in developing new technologiesfor producing liquid biofuels has been slow in developing, especiallyfor liquid fuel products that fit within the current infrastructure.Although a variety of fuels can be produced from biomass resources, suchas ethanol, methanol, biodiesel, Fischer-Tropsch diesel, and gaseousfuels, such as hydrogen and methane, these fuels require either newdistribution technologies and/or combustion technologies appropriate fortheir characteristics. The production of these fuels also tend to beexpensive and raise questions with respect to their net carbon savings.

Ethanol, for example, is made by converting the carbohydrate frombiomass into sugar, which is then converted into ethanol in afermentation process similar to brewing beer. Ethanol is the most widelyused biofuel today with current capacity of 4.3 billion gallons per yearbased on starch crops, such as corn. Ethanol, however, has verysubstantial disadvantages with respect its energy value as a fuelrelative to the amount of energy needed to produce it. Ethanol producedby fermentation contains large amounts of water, typically comprisingonly about 5 percent of ethanol by volume in the water/alcoholfermentation product. The removal of this water is highlyenergy-consuming, and often requires the use of natural gas as a heatsource. Ethanol also has less energy content than gasoline, which meansthat it takes more fuel to go the same distance. Ethanol is verycorrosive to fuel systems and cannot be transported in petroleumpipelines. As a result, ethanol is transported over-the-road in tanktrucks, which increases its overall cost and energy consumption. Whenconsidering the total energy consumed by farm equipment, cultivation,planting, fertilizers, pesticides, herbicides, petroleum-basedfungicides, irrigation systems, harvesting, transportation to processingplants, fermentation, distillation, drying, transport to fuel terminalsand retail pumps, and lower ethanol fuel energy content, the net energycontent value added and delivered to consumers is very small.

Biodiesel is another potential energy source. Biodiesel can be made fromvegetable oil, animal fats, waste vegetable oils, microalgae oils orrecycled restaurant greases, and is produced through a process in whichorganically derived oils are combined with alcohol (ethanol or methanol)in the presence of a catalyst to form ethyl or methyl ester. Thebiomass-derived ethyl or methyl esters can then be blended withconventional diesel fuel or used as a neat fuel (100% biodiesel).Biodiesel is also expensive to manufacture, and poses various issues inits use and combustion. For example, biodiesel is not suitable for usein lower temperatures and requires special handling to avoid gelling incold temperatures. Biodiesel also tends to provide higher nitrogen oxideemissions, and cannot be transported in petroleum pipelines.

Biomass can also be gasified to produce a synthesis gas composedprimarily of hydrogen and carbon monoxide, also called syngas orbiosyngas. Syngas produced today is used directly to generate heat andpower, but several types of biofuels may be derived from syngas.Hydrogen can be recovered from syngas, or it can be catalyticallyconverted to methanol. The gas can also be run through a biologicalreactor to produce ethanol or converted using Fischer-Tropsch catalystinto a liquid stream with properties similar to diesel fuel, calledFischer-Tropsch diesel. These processes are expensive and generate fuelsthat are not easily assimilated in current transportation technology.Processes capable of converting biomass using catalytic techniques wouldbe especially advantageous due to its familiarity within the currentfuel industry.

SUMMARY OF THE INVENTION

The invention provides methods, reactor systems and catalysts forproducing C₄₊ compounds (e.g., C₄₊ alcohols, C₄₊ ketones, C₄₊ alkanes,C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊ cycloalkenes, aryls, fused aryls, andmixtures thereof) from oxygenated hydrocarbons. In one embodiment, themethod involves (1) catalytically reacting, in an aqueous liquid phaseand/or a vapor phase, H₂ and water soluble oxygenated hydrocarbonscomprising a C₁₊O₁₊ hydrocarbon in the presence of a deoxygenationcatalyst at a deoxygenation temperature and deoxygenation pressure toproduce an oxygenate comprising a C₁₊O₁₋₃ hydrocarbon; and (2)catalytically reacting in the liquid and/or vapor phase the oxygenate inthe presence of a condensation catalyst at a condensation temperatureand condensation pressure to produce the C₄₊ compound. The hydrogen maybe in situ generated H₂, external H₂, supplemental H_(2,) or acombination thereof.

One aspect of the invention is a method of making a C₄₊ compoundcomprising the steps or acts of providing water and a water solubleoxygenated hydrocarbon comprising a C₁₊O₁₊ hydrocarbon in an aqueousliquid phase and/or a vapor phase, providing H₂, catalytically reactingin the liquid and/or vapor phase the oxygenated hydrocarbon with the H₂in the presence of a deoxygenation catalyst at a deoxygenationtemperature and deoxygenation pressure to produce an oxygenatecomprising a C₁₊O₁₋₃ hydrocarbon in a reaction stream, and catalyticallyreacting in the liquid and/or vapor phase the oxygenate in the presenceof an acid/base catalyst at a condensation temperature and condensationpressure to produce the C₄₊ compound, wherein the C₄₊ compound comprisesa member selected from the group consisting of C₄₊ alcohol, C₄₊ ketone,C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊ cycloalkene, aryl, fusedaryl, and a mixture thereof.

In one exemplary embodiment, the H₂ comprises in situ generated H₂,external H₂, recycled H₂, or a combination thereof. In another exemplaryembodiment, the H₂ comprises in situ generated H₂ produced bycatalytically reacting in a liquid phase and/or vapor phase a portion ofthe water and oxygenated hydrocarbon in the presence of an aqueous phasereforming catalyst at a reforming temperature and reforming pressure toproduce in situ generated H₂. In another exemplary embodiment, the stepof catalytically reacting the oxygenated hydrocarbon with H₂ in thepresence of the deoxygenation catalyst is conducted in the presence ofan insignificantly effective amount of external H₂. In another exemplaryembodiment, the molar ratio of the total oxygen atoms in the oxygenatedhydrocarbons to the total hydrogen atoms in the external H₂ is less than1:1.

The oxygenated hydrocarbons may be any water-soluble oxygenatedhydrocarbon having one or more carbon atoms and at least one oxygen atom(C₁₊O₁₊ hydrocarbons). In one exemplary embodiment, the oxygenatedhydrocarbon comprises polysaccharides, disaccharides, monosaccharides,cellulose derivatives, lignin derivatives, hemicellulose, sugars, sugaralcohols or a mixture thereof. In another exemplary embodiment, theoxygenated hydrocarbon comprises a C₁₋₁₂O₁₋₁₁ hydrocarbon, or a C₁₋₆O₁₋₆hydrocarbon. In yet another exemplary embodiment, the C₁₋₁₂O₁₋₁₁hydrocarbon comprises a sugar alcohol, sugar, monosaccharide,disaccharide, alditol, cellulosic derivative, lignocellulosicderivative, glucose, fructose, sucrose, maltose, lactose, mannose,xylose, arabitol, erythritol, glycerol, isomalt, lactitol, malitol,mannitol, sorbitol, xylitol, or a mixture thereof. In another exemplaryembodiment, the oxygenated hydrocarbon further comprises recycled C₁₊O₁₊hydrocarbon.

The oxygenates may be any hydrocarbon having 1 or more carbon atoms andbetween 1 and 3 oxygen atoms (referred to herein as C₁₊O₁₋₃hydrocarbons). In one exemplary embodiment, the oxygenate comprises analcohol, ketone, aldehyde, furan, diol, triol, hydroxy carboxylic acid,carboxylic acid, or a mixture thereof. In another exemplary embodiment,the oxygenate comprises methanol, ethanol, n-propyl alcohol, isopropylalcohol, butyl alcohol, pentanol, hexanol, cyclopentanol, cyclohexanol,2-methylcyclopentanol, hydroxyketones, cyclic ketones, acetone,propanone, butanone, pentanone, hexanone, 2-methyl-cyclopentanone,ethylene glycol, 1,3-propanediol, propylene glycol, butanediol,pentanediol, hexanediol, methylglyoxal, butanedione, pentanedione,diketohexane, hydroxyaldehydes, acetaldehyde, propionaldehyde,butyraldehyde, pentanal, hexanal, formic acid, acetic acid, propionicacid, butanoic acid, pentanoic acid, hexanoic acid, lactic acid,glycerol, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol,2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran,2-ethyl-tetrahydrofuran, 2-methyl furan, 2,5-dimethyl furan, 2-ethylfuran, hydroxylmethylfurfural, 3-hydroxytetrahydrofuran,tetrahydro-3-furanol, 5-hydroxymethyl-2(5H)-furanone,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol,1-(2-furyl)ethanol, and hydroxymethyltetrahydrofurfural, isomersthereof, or combinations thereof. In yet another exemplary embodiment,the oxygenate further comprises recycled C₁₊O₁₋₃ hydrocarbon.

The C₄₊ compound comprises a member selected from the group consistingof C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊cycloalkene, aryl, fused aryl, and a mixture thereof. In one exemplaryembodiment, the C₄₊ alkane comprises a branched or straight chain C₄₋₃₀alkane, or a branched or straight chain C₄₋₉, C₇₋₁₄, C₁₂₋₂₄ alkane, or amixture thereof. In another exemplary embodiment, the C₄₊ alkenecomprises a branched or straight chain C₄₋₃₀ alkene, or a branched orstraight chain C₄₋₉, C₇₋₁₄, C₁₂₋₂₄ alkene, or a mixture thereof. Inanother exemplary embodiment, the C₅₊ cycloalkane comprises amono-substituted or multi-substituted C₅₊ cycloalkane, and at least onesubstituted group is a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, abranched C₃₊ alkylene, a straight chain C₁₊ alkylene, a phenyl, or acombination thereof, or a branched C₃₋₁₂ alkyl, a straight chain C₁₋₁₂alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₁₋₁₂ alkylene, aphenyl, or a combination thereof, or a branched C₃₋₄ alkyl, a straightchain C₁₋₄ alkyl, a branched C₃₋₄ alkylene, straight chain C₁₋₄alkylene, a phenyl, or a combination thereof. In another exemplaryembodiment, the C₅₊ cycloalkene comprises a mono-substituted ormulti-substituted C₅₊ cycloalkene, and at least one substituted group isa branched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊alkylene, a straight chain C₂₊ alkylene, a phenyl, or a combinationthereof, or a branched C₃₋₁₂ alkyl, a straight chain C₁₋₁₂ alkyl, abranched C₃₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene, a phenyl, or acombination thereof, or a branched C₃₋₄ alkyl, a straight chain C₁₋₄alkyl, a branched C₃₋₄ alkylene, straight chain C₂₋₄ alkylene, a phenyl,or a combination thereof. In another exemplary embodiment, the arylcomprises an unsubstituted aryl, or a mono-substituted ormulti-substituted aryl, and at least one substituted group is a branchedC₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene, astraight chain C₂₊ alkylene, a phenyl, or a combination thereof, or abranched C₃₋₁₂ alkyl, a straight chain C₁₋₁₂ alkyl, a branched C₃₋₁₂alkylene, a straight chain C₂₋₁₂ alkylene, a phenyl, or a combinationthereof, or a branched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, abranched C₃₋₄ alkylene, a straight chain C₂₋₄ alkylene, a phenyl, or acombination thereof. In another exemplary embodiment, the fused arylcomprises an unsubstituted fused aryl, or a mono-substituted ormulti-substituted fused aryl, and at least one substituted group is abranched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene,a straight chain C₂₊ alkylene, a phenyl, or a combination thereof, or abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, a straight chain C₂₋₄ alkylene, a phenyl, or a combinationthereof. In another exemplary embodiment, the C₄₊ alcohol comprises acompound according to the formula R¹—OH, wherein R¹ is a branched C₄₊alkyl, straight chain C₄₊ alkyl, a branched C₄₊ alkylene, a straightchain C₄₊ alkylene, a substituted C₅₊ cycloalkane, an unsubstituted C₅₊cycloalkane, a substituted C₅₊ cycloalkene, an unsubstituted C₅₊cycloalkene, an aryl, a phenyl, or a combination thereof. In anotherexemplary embodiment of method of making the C₄₊ compound, the C₄₊ketone comprises a compound according to the formula

wherein R³ and R⁴ are independently a branched C₃₊ alkyl, a straightchain C₁₊ alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene,a substituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, asubstituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl,a phenyl, or a combination thereof.

In another exemplary embodiment of the method, the condensation catalystcomprises a carbide, nitride, zirconia, alumina, silica,aluminosilicate, phosphate, zeolite, titanium oxide, zinc oxide,vanadium oxide, cerium oxide, lanthanum oxide, yttrium oxide, scandiumoxide, magnesium oxide, barium oxide, calcium oxide, hydroxide,heteropolyacid, inorganic acid, acid modified resin, base modifiedresin, or a combination thereof. The condensation catalyst furthercomprises a modifier, such as Ce, La, Y, Sc, Li, Na, K, Rb, Cs, Mg, Ca,Sr, Ba, P, B, Bi, or a combination thereof. The condensation catalystmay also further comprises a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co,Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloythereof, or a combination thereof.

In one exemplary embodiment, the condensation reaction is performedusing a multi-functional catalyst having both acid and basefunctionality. In one exemplary embodiment, the acid-base catalystcomprises a hydrotalcite, zinc-aluminate, phosphate, Li, Na, K, Cs, B,Rb, Mg, Ca, Sr, Si, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn, Cr, an alloythereof, or a combination thereof. The acid-base catalyst furthercomprises an oxide of any of the following: Ti, Zr, V, Nb, Ta, Mo, Cr,W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn, Sn, Cd, P, or acombination thereof. The acid-base catalyst may further comprises ametal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, an alloy thereof, or a combinationthereof.

In another exemplary embodiment of the method, the acid-base catalystcomprises a binary oxide, such as MgO and Al₂O₃ combination, a MgO andZrO_(2,) combination, or a ZnO and Al₂O₃ combination. The acid-basecatalyst may further comprises a metal, such as Cu, Pt, Pd, Ni, or acombination thereof.

In another exemplary embodiment of the method, the acid-base catalystcomprises a zeolite, such as ZSM-5, ZSM-11, ZSM-12, ZSM-22, ZSM-23,ZSM-35, ZSM-48 or a combination thereof. The acid-base catalyst furthercomprises a metal, such as Cu, Pt, Pd, Ni, or a combination thereof.

The deoxygenation catalyst is preferably a heterogeneous catalyst havingone or more materials capable of catalyzing a reaction between hydrogenand the oxygenated hydrocarbon to remove one or more of the oxygen atomsfrom the oxygenated hydrocarbon to produce alcohols, ketones, aldehydes,furans, carboxylic acids, hydroxy carboxylic acids, diols and triols. Inone exemplary embodiment, the deoxygenation catalyst comprises a supportand Re, Cu, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo, Ag, Au, an alloythereof, or a combination thereof. In another exemplary embodiment, thedeoxygenation catalyst further comprises Mn, Cr, Mo, W, V, Nb, Ta, Ti,Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, or acombination thereof. In one exemplary embodiment, the support comprisesa nitride, carbon, silica, alumina, zirconia, titania, vanadia, ceria,boron nitride, heteropolyacid, kieselguhr, hydroxyapatite, zinc oxide,chromia, or a mixture thereof. In another exemplary embodiment, thesupport is a hydrogen peroxide treated carbon. In another exemplaryembodiment, the support is modified by treating the support with amodifier being silanes, alkali compounds, alkali earth compounds, orlanthanides. In another exemplary embodiment, the support comprisescarbon nanotubes, carbon fullerenes, and zeolites. In another exemplaryembodiment, the deoxygenation catalyst and the condensation catalyst areatomically identical.

The APR catalyst is preferably a heterogeneous catalyst capable ofcatalyzing the reaction of water and oxygenated hydrocarbons to form H₂.In one exemplary embodiment, the aqueous phase reforming catalystcomprises a support and Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, an alloythereof, or a combination thereof. In another exemplary embodiment, theaqueous phase reforming catalyst further comprises Cu, B, Mn, Re, Cr,Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al,Ga, In, Tl, an alloy thereof, or a combination thereof. In anotherexemplary embodiment, the support comprises any one of the abovesupports described for the deoxygenation catalyst. In another exemplaryembodiment, one or more of the aqueous phase reforming catalyst,deoxygenation catalyst, and condensation catalyst are atomicallyidentical. In yet another exemplary embodiment, the aqueous phasereforming catalyst and deoxygenation catalyst comprise Pt alloyed oradmixed with Ni, Ru, Cu, Fe, Rh, Re, alloys thereof, or a combinationthereof. In another exemplary embodiment, the aqueous phase reformingcatalyst and deoxygenation catalyst comprise Ru alloyed or admixed withGe, Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys thereof, or a combinationthereof. In another exemplary embodiment, the aqueous phase reformingcatalyst comprises Ni alloyed or admixed with Sn, Ge, Bi, B, Cu, Re, Ru,Fe, alloys thereof, or a combination thereof.

In general, the APR reaction should be conducted at a temperature wherethe thermodynamics are favorable. In one exemplary embodiment, thereforming temperature is in the range of about 100° C. to about 450° C.,and the reforming pressure is a pressure where the water and theoxygenated hydrocarbon are gaseous. In another exemplary embodiment, thereforming temperature is in the range of about 100° C. to about 300° C.,and the reforming pressure is a pressure where the water and theoxygenated hydrocarbon are gaseous. In yet another exemplary embodiment,the reforming temperature is in the range of about 80° C. to 400° C.,and the reforming pressure is a pressure where the water and theoxygenated hydrocarbon are liquid.

In general, the deoxygenation reaction should be conducted at atemperature where the thermodynamics are favorable. In one exemplaryembodiment, the deoxygenation temperature is in the range of about 100°C. to 600° C., and the deoxygenation pressure is at least 0.1atmosphere. In another exemplary embodiment, the deoxygenationtemperature is in the range of about 80° C. to about 300° C., and thedeoxygenation pressure is a pressure where the water and the oxygenatedhydrocarbon are liquid. In yet another exemplary embodiment, thedeoxygenation temperature is in the range of about 200° C. to about 280°C., and the deoxygenation pressure is a pressure where the water and theoxygenated hydrocarbon are liquid. In another exemplary embodiment, thedeoxygenation temperature is in the range of about 100° C. to 600° C.,and the deoxygenation pressure is a pressure where the water and theoxygenated hydrocarbon are gaseous. In another exemplary embodiment, thedeoxygenation temperature is in the range of about 200° C. to 280° C.,and the deoxygenation pressure is a pressure where the water and theoxygenated hydrocarbon are gaseous. In another exemplary embodiment, thereforming temperature and deoxygenation temperature is in the range ofabout 100° C. to 450° C., and the reforming pressure and deoxygenationpressure is in the range of about 72 psig to 1300 psig. In anotherexemplary embodiment, the reforming temperature and deoxygenationtemperature is in the range of about 120° C. to 300° C., and thereforming pressure and deoxygenation pressure is in the range of about72 psig to 1200 psig. In another exemplary embodiment, the reformingtemperature and deoxygenation temperature is in the range of about 200°C. to 280° C., and the reforming pressure and deoxygenation pressure isin the range of about 200 psig to 725 psig.

In general, the condensation reaction should be conducted at atemperature where the thermodynamics are favorable. In one exemplaryembodiment, the condensation temperature is in the range of about 80° C.to 500° C., and the condensation pressure is in the range of about 0psig to 1200 psig. In another exemplary embodiment, the condensationtemperature is in the range of about 125° C. to 450° C., and thecondensation pressure is at least 0.1 atm. In another exemplaryembodiment, the condensation temperature is in the range of about 125°C. to 250° C., and the condensation pressure is in the range of about 0psig to 700 psig. In another exemplary embodiment, the condensationtemperature is in the range of about 250° C. to 425° C.

In an exemplary embodiment, the reaction stream further comprises water,and the method further comprises the step or act of dewatering thereaction stream prior to reacting the oxygenate in the presence of thecondensation catalyst.

In an exemplary embodiment, the method further comprises the step or actof catalytically reacting in the liquid and/or vapor phase a sugar,sugar alcohol or polyhydric alcohol with H₂ in the presence of ahydrogenolysis catalyst at a hydrogenolysis temperature andhydrogenolysis pressure to produce the oxygenated hydrocarbon. Inanother embodiment, the hydrogenolysis temperature is at least 110° C.and the hydrogenolysis pressure is in the range of about 10 psig to 2400psig. In another exemplary embodiment, the hydrogenolysis temperature isin the range of about 110° C. to 300° C. The hydrogenolysis catalystgenerally comprises phosphate, Cr, Mo, W, Re, Mn, Cu, Cd, Fe, Ru, Os,Ir, Co, Rh, Pt, Pd, Ni, alloys thereof, or a combination thereof. Inanother exemplary embodiment, the hydrogenolysis catalyst furthercomprises Au, Ag, Zn, Sn, Bi, B, Cr, Mn, O, alloys thereof, or acombination thereof. In another exemplary embodiment, the hydrogenolysiscatalyst further comprises an alkaline earth metal oxide. In anotherexemplary embodiment, the hydrogenolysis catalyst further comprises anyone of the above supports. In another exemplary embodiment, the H₂comprises in situ generated H₂, external H₂, recycled H₂, or acombination thereof.

In another exemplary embodiment, the method further comprises the stepor act of catalytically reacting in the liquid and/or vapor phase asugar, furfural, carboxylic acid, ketone, or furan with H₂ in thepresence of a hydrogenation catalyst at a hydrogenation temperature andhydrogenation pressure to produce the oxygenated hydrocarbon. In anotherembodiment, the hydrogenation temperature is in the range of about 80°C. to 250° C., and the hydrogenation pressure is in the range of about100 psig to 2000 psig. The hydrogenation catalyst generally comprises asupport and Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, Re, Cu, alloys thereof,or a combination thereof. In another exemplary embodiment, thehydrogenation catalyst further comprises Ag, Au, Cr, Zn, Mn, Sn, Bi, Mo,W, B, P, alloys thereof, or a combination thereof. In another exemplaryembodiment, the support comprises any one of the above supports. Inanother exemplary embodiment, the H₂ comprises in situ generated H₂,external H₂, recycled H₂, or a combination thereof.

In another exemplary embodiment, the method further comprises the stepor act of catalytically reacting the C₄₊ compound in the liquid phaseand/or vapor phase in the presence of a finishing catalyst at afinishing temperature and a finishing pressure. The finishing catalystgenerally comprises a support and Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir,Os, an alloy thereof, or a combination thereof. In another exemplaryembodiment, the finishing catalyst further comprises a modifier beingAu, Ag, Cr, Zn, Mn, Sn, Cu, Cr, Bi, alloys thereof, or a combinationthereof. In another exemplary embodiment, the support is any one of theabove described supports.

Another aspect of the invention is a method of making a C₄₊ compoundcomprising the steps or acts of providing water and a water solubleoxygenated hydrocarbon comprising a C₁₊O₁₊ hydrocarbon in an aqueousliquid phase and/or a vapor phase, catalytically reacting a portion ofthe water and oxygenated hydrocarbon in the liquid phase and/or vaporphase in the presence of an aqueous phase reforming catalyst at areforming temperature and a reforming pressure to produce in situgenerated H₂, catalytically reacting in the liquid and/or vapor phasethe oxygenated hydrocarbon with the in situ generated H₂ in the presenceof a deoxygenation catalyst at a deoxygenation temperature anddeoxygenation pressure to produce an oxygenate comprising a C₁₊O₁₋₃hydrocarbon in a reaction stream, and, catalytically reacting in theliquid and/or vapor phase the oxygenate in the presence of acondensation catalyst comprising an acid/base catalyst at a condensationtemperature and condensation pressure to produce the C₄₊ compound,wherein the C₄₊ compound comprises a member selected from the groupconsisting of C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊cycloalkane, C₅₊ cycloalkene, aryl, fused aryl, and a mixture thereof.

In another exemplary embodiment, the method further comprises the stepsor acts of providing supplemental H₂, and, catalytically reacting aportion of the oxygenated hydrocarbon with supplemental H₂ in thepresence of the deoxygenation catalyst to produce the oxygenate.

In another exemplary embodiment, the method further comprises the stepor act of catalytically reacting in the liquid and/or vapor phase sugar,furfural, carboxylic acid, ketone, or furan with in situ generated H₂and/or supplemental H₂ in the presence of a hydrogenation catalyst at ahydrogenation temperature and hydrogenation pressure to produce theoxygenated hydrocarbon. In another exemplary embodiment, thehydrogenation temperature is in the range of about 80° C. to 250° C.,and the hydrogenation pressure is in the range of about 100 psig to 2000psig. In another exemplary embodiment, the supplemental H₂ comprisesexternal H₂, recycled H₂ or a combination thereof.

In another exemplary embodiment, the method further comprises the stepor act of catalytically reacting in the liquid and/or vapor phase asugar, sugar alcohol or polyhydric alcohol with in situ generated H₂and/or supplemental H₂ in the presence of a hydrogenolysis catalyst at ahydrogenolysis temperature and hydrogenolysis pressure to produce theoxygenated hydrocarbon. In another exemplary embodiment, thehydrogenolysis temperature is in the range of about 110° C. to 300° C.In another exemplary embodiment, the supplemental H₂ comprises externalH₂, recycled H₂ or a combination thereof.

In another exemplary embodiment, the method includes any of the abovedescribed water soluble oxygenated hydrocarbons, oxygenates, C₄₊compounds, acid/base catalysts, deoxygenation catalysts, aqueous phasereforming catalysts. In another exemplary embodiment, one or more of thedeoxygenation catalyst, aqueous phase reforming catalyst, andcondensation catalyst are atomically identical. In another exemplaryembodiment, the aqueous phase reforming catalyst and deoxygenationcatalyst comprise Pt alloyed or admixed with Ni, Ru, Cu, Fe, Rh, Re,alloys thereof, or a combination thereof. In another exemplaryembodiment, the aqueous phase reforming catalyst and deoxygenationcatalyst comprise Ru alloyed or admixed with Ni, Sn, Cu, Fe, Rh, Pt,alloys thereof, or a combination thereof. In another exemplaryembodiment, the aqueous phase reforming catalyst comprises Ni alloyed oradmixed with Cu, Re, Ru, Fe, alloys thereof, or a combination thereof.In another exemplary embodiment, the hydrogenation catalyst comprisesany one of the above hydrogenation catalysts. In another exemplaryembodiment, the hydrogenolysis catalyst comprises any of the abovehydrogenolysis catalysts.

In general, the reactions should be conducted at temperatures andpressures where the thermodynamics are favorable. In one exemplaryembodiment, the reforming temperature is in the range of about 100° C.to about 450° C., and the reforming pressure is a pressure where thewater and the oxygenated hydrocarbon are gaseous. In another exemplaryembodiment, the reforming temperature is in the range of about 80° C. to400° C., and the reforming pressure is a pressure where the water andthe oxygenated hydrocarbon are liquid. In another exemplary embodiment,the deoxygenation temperature is in the range of about 100° C. to 600°C., and the deoxygenation pressure is at least 0.1 atmosphere. Inanother exemplary embodiment, the reforming temperature anddeoxygenation temperature is in the range of about 100° C. to 450° C.,and the reforming pressure and deoxygenation pressure is in the range ofabout 72 psig to 1300 psig. In another exemplary embodiment, thecondensation temperature is in the range of about 80° C. to 500° C., andthe condensation pressure is at least 0.1 atm.

In another exemplary embodiment, the reaction stream further compriseswater, and, the method further comprises the step or act of dewateringthe reaction stream prior to reacting the oxygenate in the presence ofthe condensation catalyst.

In another exemplary embodiment, the step of catalytically reacting theoxygenated hydrocarbon with in situ generated H₂ in the presence of thedeoxygenation catalyst is conducted in the presence of aninsignificantly effective amount of external H₂. In another exemplaryembodiment, the molar ratio of the total oxygen atoms in the oxygenatedhydrocarbons to the total hydrogen atoms in the external H₂ is less than1:1.

In another exemplary embodiment, the method further comprises the stepor act of catalytically reacting the C₄₊ compound in the liquid phaseand/or vapor phase in the presence of a finishing catalyst at afinishing temperature and a finishing pressure, wherein the finishingcatalyst comprises a support and Cu, Ni, Fe, Co, Ru, Pd, Rh, Pt, Ir, Os,an alloy thereof, or a combination thereof. In another exemplaryembodiment, the finishing catalyst further comprises a modifier beingAu, Ag, Cr, Zn, Mn, Sn, Cu, Cr, Bi, alloys thereof, or a combinationthereof. In another exemplary embodiment, the support comprises any oneof the above supports.

In another exemplary embodiment, the method is performed in a reactorsystem comprising one or more reactor vessels, wherein the reactorsystem is adapted to be configured as continuous flow, batch,semi-batch, multi-system or a combination thereof. In another exemplaryembodiment, the reactor system further comprises one or more of afluidized catalytic bed, a swing bed, fixed bed, moving bed or acombination thereof, wherein each bed is adapted to be housed within areactor vessel. In another exemplary embodiment, the method is performedin the continuous flow reactor system at steady-state equilibrium. Inanother exemplary embodiment, the reactor system further comprises areforming bed adapted to contain the aqueous phase reforming catalyst, adeoxygenation bed adapted to contain the deoxygenation catalyst, and, acondensation bed adapted to contain the condensation catalyst. Inanother exemplary embodiment, the reforming bed and deoxygenation bedare oriented in a stacked, side-by-side or parallel configuration, andthe reforming and deoxygenation beds are housed within a single reactorvessel. In another exemplary embodiment, the reforming bed is housedwithin a reforming reactor vessel, and the deoxygenation bed is housedwithin a deoxygenation reactor vessel. In another exemplary embodiment,the condensation bed is housed within a condensation reactor vessel. Inanother exemplary embodiment, the single reactor vessel is furtheradapted to house the condensation bed. In another exemplary embodiment,the reforming bed, deoxygenation bed, and condensation bed are orientedin a stacked, side-by-side or parallel configuration within the singlereactor vessel. In another exemplary embodiment, the continuous flowreactor system is oriented to provide horizontal, vertical or diagonalflow. In another exemplary embodiment, the deoxygenation bed is housedwithin a deoxygenation reactor vessel providing up-flow, and wherein thecondensation bed is housed within a condensation reactor vesselproviding down-flow. In another exemplary embodiment, each catalyticreaction occurs at steady-state equilibrium.

Another aspect of the invention is a method of making a C₄₊ compoundcomprising the steps or acts of providing an aqueous solution comprisingwater and a member selected from the group consisting of a sugar,furfural, carboxylic acid, ketone, furan, and a combination thereof;catalytically reacting in a liquid and/or vapor phase the sugar,furfural, carboxylic acid, ketone, furan, or combination thereof, withH₂ in the presence of a hydrogenation catalyst at a hydrogenationtemperature and hydrogenation pressure to produce an oxygenatedhydrocarbon comprising a C₁₊O₁₋₃ hydrocarbon, catalytically reacting aportion of the water and oxygenated hydrocarbon in the liquid phaseand/or vapor phase in the presence of an aqueous phase reformingcatalyst at a reforming temperature and a reforming pressure to producein situ generated H₂, catalytically reacting in the liquid and/or vaporphase the oxygenated hydrocarbon with the in situ generated H₂ in thepresence of a deoxygenation catalyst at a deoxygenation temperature anddeoxygenation pressure to produce an oxygenate comprising a C₁₊O₁₋₃hydrocarbon, and, catalytically reacting in the liquid and/or vaporphase the oxygenate in the presence of a condensation catalystcomprising an acid/base catalyst at a condensation temperature andcondensation pressure to produce the C₄₊ compound, wherein the C₄₊compound comprises a member selected from the group consisting of C₄₊alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊cycloalkene, aryl, fused aryl, and, a mixture thereof.

In another exemplary embodiment, the method further comprises providingsupplemental H₂ comprising external H₂, recycled H₂ or a combinationthereof, and reacting the supplemental H₂ with the sugar, furfural,carboxylic acid, ketone, furan, or combination thereof and/or with theC₁₊O₁₊ oxygenated hydrocarbon.

In another exemplary embodiment, the oxygenated hydrocarbon comprisesany of the above oxygenated hydrocarbons; the oxygenate comprises any ofthe above oxygenates; the C₄₊ compound comprises any of the above C₄₊compounds; the hydrogenation catalyst comprises any of the abovehydrogenation catalysts; the aqueous phase reforming catalyst comprisesany of the above aqueous phase reforming catalysts; the condensationcatalyst comprises any of the above acid/base condensation catalysts;and, the deoxygenation catalyst comprises any of the above deoxygenationcatalysts.

In another exemplary embodiment, one or more of the hydrogenationcatalyst, aqueous phase reforming catalyst, deoxygenation catalyst, andcondensation catalyst are atomically identical.

Another aspect of the invention is a method of making a C₄₊ compoundcomprising providing an aqueous solution comprising water and apolysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar,sugar alcohol, or a combination thereof; catalytically reacting in aliquid and/or vapor phase the sugar, sugar alcohol, polysaccharide,disaccharide, monosaccharide, polyhydric alcohol, or combination, withH₂ in the presence of a hydrogenolysis catalyst at a hydrogenolysistemperature and hydrogenolysis pressure to produce an oxygenatedhydrocarbon comprising a C₁₊O₁₊ hydrocarbon, catalytically reacting aportion of the water and oxygenated hydrocarbon in the liquid phaseand/or vapor phase in the presence of an aqueous phase reformingcatalyst at a reforming temperature and a reforming pressure to producein situ generated H₂, catalytically reacting in the liquid and/or vaporphase the oxygenated hydrocarbon with the in situ generated H₂ in thepresence of a deoxygenation catalyst at a deoxygenation temperature anddeoxygenation pressure to produce an oxygenate comprising a C₁₊O₁₋₃hydrocarbon, and, catalytically reacting in the liquid and/or vaporphase the oxygenate in the presence of a condensation catalystcomprising an acid/base catalyst at a condensation temperature andcondensation pressure to produce the C₄₊ compound, wherein the C₄₊compound comprises a member selected from the group consisting of C₄₊alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊ cycloalkane, C₅₊cycloalkene, aryl, fused aryl, and a mixture thereof.

In another exemplary embodiment, the method further comprises the stepsor acts of providing supplemental H₂ comprising external H₂, recycled H₂or a combination thereof, and, reacting the supplemental H₂ with thepolysaccharide, disaccharide, monosaccharide, polyhydric alcohol, sugar,sugar alcohol, or combination thereof and/or with the C₁₊O₁₋₃ oxygenatedhydrocarbon.

In another exemplary embodiment, the oxygenated hydrocarbon comprisesany of the above oxygenated hydrocarbons; the oxygenate comprises any ofthe above oxygenates; the C₄₊ compound comprises any of the above C₄₊compounds; the hydrogenolysis catalyst comprises any of the abovehydrogenolysis catalysts; the aqueous phase reforming catalyst comprisesany of the above aqueous phase reforming catalysts; the condensationcatalyst comprises any of the above acid/base condensation catalysts;and, the deoxygenation catalyst comprises any of the above deoxygenationcatalysts.

In another exemplary embodiment, one or more of the hydrogenolysiscatalyst, aqueous phase reforming catalyst, deoxygenation catalyst, andcondensation catalyst are atomically identical.

Another aspect of the invention is a method of making a C₄₊ compoundcomprising the steps or acts of providing an oxygenate comprising aC₁₊O₁₋₃ hydrocarbon in an aqueous liquid phase and/or a vapor phase,and, catalytically reacting in the liquid and/or vapor phase theoxygenate in the presence of a condensation catalyst at a condensationtemperature and condensation pressure to produce the C₄₊ compound,wherein the C₄₊ compound comprises a member selected from the groupconsisting of C₄₊ alcohol, C₄₊ ketone, C₄₊ alkane, C₄₊ alkene, C₅₊cycloalkane, C₅₊ cycloalkene, aryl, fused aryl, and a mixture thereof.

In another exemplary embodiment, the oxygenate comprises any of theabove oxygenates; the C₄₊ compound comprises any of the above C₄₊compounds; the condensation catalyst comprises any of the aboveacid/base condensation catalysts; and, the deoxygenation catalystcomprises any of the above deoxygenation catalysts.

Another aspect of the invention is a composition comprising one or moreC₄₊ compounds made by any one of the above methods. In an exemplaryembodiment of the composition, the composition comprises benzene,toluene, xylene, ethyl benzene, para xylene, meta xylene, ortho xylene,C₉ aromatics, an isomer thereof or a mixture thereof.

In an exemplary embodiment of the method of making hydrocarbons, ketonesor alcohols, the method further includes the reactions steps eachproceeding at steady-state equilibrium. In an exemplary embodiment ofthe reactor system for making hydrocarbons, the system is adapted toproduce hydrocarbons at steady-state equilibrium.

BRIEF DESCRIPTION OF THE DRAWINGS OF THE EXEMPLARY EMBODIMENTS

FIG. 1 is a flow diagram illustrating various production pathwaysassociated with the present invention.

FIG. 2 illustrates potential chemical routes that allow carbohydrates,such as sugars, to be converted to non-oxygenated hydrocarbons.

FIG. 3 is an illustration of various reaction pathways involved in thedeoxygenation of sorbitol to oxygenates and APR hydrogen.

FIG. 4 is an illustration of the thermodynamic equilibrium along thereaction pathway for converting acetone to 2-methyl pentane at 100° C.and 400° C.

FIG. 5 is a graph illustrating the equilibrium constants associated withthe intermediate reaction products and the overall conversion for thereaction of 2 moles of acetone with 3 moles of hydrogen to form 1 moleof 2-methylpentane and 2 moles of water.

FIG. 6 is a flow diagram illustrating a reactor system configured toallow for the recycle of hydrogen, oxygenates and oxygenatedhydrocarbons.

FIG. 7 is a flow diagram illustrating a reactor system configured toallow for the use of air or an oil as a temperature control element.

FIG. 8 a flow diagram illustrating a reactor system for the presentinvention.

FIG. 9 is a flow diagram illustrating a reactor system utilizing tworeactors.

FIG. 10 is a flow diagram illustrating a reactor system utilizing twofeedstock lines.

FIG. 11 is an illustration of a reactor useful in practicing the presentinvention.

FIG. 12 is a graph illustrating the carbon distribution ofmono-oxygenates produced from glycerol.

FIG. 13 is a graph illustrating the axial temperature profile for areactor when used to produce compounds from a feedstock of oxygenatedhydrocarbons.

FIG. 14 is a graph illustrating the percentage of feed carbon exiting asoxygenates from the conversion of an oxygenate feed stream to C₅₊compounds as a function of time.

FIG. 15 is a graph illustrating the percentage of feed carbon exiting asC₅₊ hydrocarbons from the conversion of an oxygenate feed stream as afunction of time.

FIG. 16 is a graph illustrating the percentage of feed carbon exiting asC₅₊ aromatic hydrocarbons from the conversion of an oxygenate feedstream as a function of time.

FIG. 17 is a graph showing the total weight percentage of paraffin andaromatic compounds derived from the conversion of a feed stream ofsucrose and xylose.

FIG. 18 is a graph illustrating the heating value of C₅₊ hydrocarbonsderived from the production of gasoline from sorbitol, as a percentageof the heating value of the feed.

FIG. 19 is a graph illustrating the percentage of carbon recovered asaromatic hydrocarbons from the production of gasoline from sorbitol,shown as a percentage of the carbon present in the feed.

DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

There exists a need for new biofuels, and especially biofuels capable ofuse in the current infrastructure, namely the same distribution systemand the same engines without the need for special modifications. Therealso exists a need for new biofuels that do not depend onmicroorganisms, enzymes or other expensive and delicate manufacturingprocesses. There is also a need for processes for converting biomass tohydrocarbon fuels having a greater amount of energy content thanethanol, and with lower energy consumption as part of the manufacturingprocess. Processes capable of converting biomass using catalytictechniques would be especially advantageous due to its familiaritywithin the current fuel industry.

The present invention relates to methods, reactor systems and catalystsfor producing hydrocarbons, ketones and alcohols from biomass-derivedoxygenated hydrocarbons, such as sugars, sugar alcohols, cellulosics,lignocelluloses, hemicelluloses, saccharides and the like. Thehydrocarbons and mono-oxygenated hydrocarbons produced are useful infuel products, such as synthetic gasoline, diesel fuel and/or jet fuels,and as industrial chemicals.

The present invention is directed to methods, reactor systems andcatalysts for producing C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊cycloalkenes, aryls, fused aryls, C₄₊ alcohols, C₄₊ ketones, andmixtures thereof (collectively referred to herein as “C₄₊ compounds”),from oxygenated hydrocarbons. The C₄₊ hydrocarbons have from 4 to 30carbon atoms and may be branched or straight chained alkanes or alkenes,or unsubstituted, mono-substituted or multi-substituted aromatics(aryls) or cycloalkanes. The C₄₊ alcohols and C₄₊ ketones may be cyclic,branched or straight chained, and have from 4 to 30 carbon atoms.Lighter fractions, primarily C₄-C₉, may be separated for gasoline use.Moderate fractions, such as C₇-C₁₄, may be separated for jet fuel, whileheavier fractions, i.e., C₁₂-C₂₄, may be separated for diesel use. Theheaviest fractions may be used as lubricants or cracked to produceadditional gasoline and/or diesel fractions. The C₄₊ compounds may alsofind use as industrial chemicals, such as xylene, whether as anintermediate or an end product.

The general process is illustrated in FIG. 1. A feedstock solutioncontaining a water-soluble oxygenated hydrocarbon having one or morecarbon atoms is reacted with hydrogen over a deoxygenation catalyst toproduce oxygenates, and then the oxygenates are reacted over acondensation catalyst under conditions of temperature and pressureeffective to cause a condensation reaction that produces the C₄₊compounds. The hydrogen may originate from any source, but is preferablyderived in situ or in parallel from biomass using aqueous phasereforming. The hydrogen and oxygenated hydrocarbons may also besupplemented with recycled hydrogen and oxygenated hydrocarbons derivedfrom the process. The oxygenated hydrocarbon may be a monosaccharide,disaccharide, polysaccharide, cellulose, hemicellulose, lignin, sugar,sugar alcohol or other polyhydric alcohols, or may be derived from thehydrogenation of a sugar, furfural, carboxylic acid, ketone, or furan,or the hydrogenolysis of a sugar, sugar alcohol, polysaccharide,monosaccharide, disaccharide or polyhydric alcohol.

One unique aspect about the present invention is that the C₄₊ compoundsare derived from biomass components using catalytic processes instead ofmicroorganisms, enzymes, high temperature gasification ortransesterification methods. The present invention can also generatehydrogen in situ to avoid reliance on external hydrogen sources, such ashydrogen generated from the steam reforming of natural gas, or theelectrolysis or thermolysis of water. The present invention alsogenerates water, which may be recycled and used in upstream processes orreturned to the environment. The present invention is also able togenerate non-condensable fuel gases for purposes of providing a heatsource within the reactor system or for external processes.

Carbohydrates are the most widely distributed, naturally occurringorganic compounds on Earth. Carbohydrates are produced duringphotosynthesis, a process in which the energy from the sun is convertedinto chemical energy by combining carbon dioxide with water to formcarbohydrates and oxygen:

The energy from sunlight is stored through this process as chemicalenergy in the form of carbohydrates in plants. The carbohydrates,especially when in a sugar form, are highly reactive compounds that arereadily oxidized by living material to generate energy, carbon dioxideand water. Plant materials store these carbohydrates either as sugars,starches, polymeric cellulose, and/or hemi-cellulose.

The presence of oxygen in the molecular structure of carbohydratescontributes to the reactivity of sugars in biological systems. Ethanolfermentation technology takes advantage of this highly reactive natureby forming ethanol at ambient temperatures. The fermentation technologyessentially de-functionalizes the highly reactive sugar to generate apartially oxidized hydrocarbon, ethanol. Ethanol, however, has verysubstantial disadvantages with respect its energy value as highlightedabove.

FIG. 2 shows potential chemical routes that allow carbohydrates, such assugars, to be converted to non-oxygenated hydrocarbons. Water solublecarbohydrates are known to react with hydrogen over catalyst(s) togenerate polyhydric alcohols, either by hydrogenation or hydrogenolysis.The hydrogen has historically been generated externally, i.e., fromnatural gas or by other processes, but can now be generated in situ orin parallel according to the present invention through the aqueous-phasereforming of the polyhydric alcohol.

The aqueous-phase reforming (APR) of the polyhydric alcohol proceedsthrough the formation of an aldehyde (shown in FIG. 2) where thealdehyde reacts over a catalyst with water to form hydrogen, carbondioxide, and a smaller polyhydric alcohol. The polyhydric alcohol canfurther react with hydrogen over a catalyst through a series ofdeoxygenation reactions to form either alcohol, ketone, or aldehydesspecies that can undergo condensation reactions to form either largercarbon number straight chain compounds, branched chain compounds, orcyclic compounds. The condensation reactions can be either acidcatalyzed, base catalyzed, or both acid and base catalyzed. Theresulting compounds may be hydrocarbons or hydrocarbons containingoxygen, the oxygen of which can be removed through the reaction withhydrogen over a catalyst. The resulting condensed products include C₄₊alcohols, C₄₊ ketones, C₄₊ alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊cycloalkenes, aryls, fused aryls, and mixtures thereof. The mixtures canbe fractionated and blended to produce the appropriate mixtures ofmolecules typically used in gasoline, jet fuel, or diesel liquid fuels,or in industrial processes.

The de-functionalization begins by reacting the glucose with hydrogen ineither a hydrogenation reaction or hydrogenolysis reaction to convertthe cyclic sugar molecule to its corresponding linear alcohol, sorbitol,or lower polyhydric alcohols, such as glycerol, propylene glycol,ethylene glycol, xylitol, among others. As indicated above, the hydrogenmay be from any source, but is preferably hydrogen generated in situ byaqueous phase reforming or excess hydrogen recycled from the reactorsystem.

During the aqueous phase reforming process, the carbohydrate firstundergoes dehydrogenation to provide adsorbed intermediates, prior tocleavage of C—C or C—O bonds. Subsequent cleavage of C—C bonds leads tothe formation of CO and H₂, with the CO then reacting with water to formCO₂ and H₂ by the water-gas shift reaction. Various APR methods andtechniques are described in U.S. Pat. Nos. 6,699,457; 6,964,757 and6,964,758; and U.S. patent application Ser. No. 11/234,727 (all toCortright et al., and entitled “Low-Temperature Hydrogen Production fromOxygenated Hydrocarbons”); and U.S. Pat. No. 6,953,873 (to Cortright etal., and entitled “Low Temperature Hydrocarbon Production fromOxygenated Hydrocarbons”); and commonly owned co-pending InternationalPatent Application No. PCT/US2006/048030 (to Cortright et al., andentitled “Catalyst and Methods for Reforming Oxygenated Compounds”), allof which are incorporated herein by reference. The term “aqueous phasereforming” and “APR” shall generically denote the reforming ofoxygenated hydrocarbons and water to yield hydrogen and carbon dioxide,regardless of whether the reactions takes place in the gaseous phase orin the condensed liquid phase. “APR H₂” shall generically refer to thehydrogen produced by the APR process.

The resulting oxygenated hydrocarbon, namely the sorbitol or glycerol,propylene glycol, ethylene glycol, xylitol, etc., are furtherdefunctionalized through deoxygenation reactions to form oxygenates,such as alcohols, ketones, aldehydes, furans, diols, triols, hydroxycarboxylic acids, and carboxylic acids for use in later condensationreactions. FIG. 3 illustrates various reaction pathways involved in thedeoxygenation of sorbitol to oxygenates and APR hydrogen. In general,without being limited to any particular theory, it is believed that thedeoxygenation reactions involves a combination of various differentreaction pathways, including without limitation: hydrodeoxygenation,consecutive dehydration-hydrogenation, hydrogenolysis, hydrogenation anddehydration reactions, resulting in the removal of oxygen from theoxygenated hydrocarbon to arrive at a hydrocarbon molecule having thegeneral formula C₁₊O₁₋₃.

The oxygenates produced are then converted into C₄₊ compounds bycondensation. Without being limited to any specific theories, it isbelieved that the acid condensation reactions generally consist of aseries of steps involving: (a) the dehydration of oxygenates to olefins;(b) oligomerization of the olefins; (c) cracking reactions; (d)cyclization of larger olefins to form aromatics; (e) paraffinisomerization; and (f) hydrogen-transfer reactions to form paraffins.Basic condensation reactions are believed to generally consist of aseries of steps involving: (1) aldol condensation to form aβ-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of theβ-hydroxyketone or β-hydroxyaldehyde to form a conjugated enone; (3)hydrogenation of the conjugated enone to form a ketone or aldehyde,which may participate in further condensation reactions or conversion toan alcohol or hydrocarbon; and (4) hydrogenation of carbonyls toalcohols, or vice-versa. Acid-base condensation reactions are believedto generally involve any of the previous acidic and/or basic reactionssteps.

In certain embodiments, the condensation reactions occur at typicalcondensation temperatures and pressures. However, in variousembodiments, it may also be more favorable to conduct the condensationreactions at temperature and/or pressure conditions that are elevated ascompared to typical condensation processes. Generally, conductingcondensation reactions under elevated conditions results in unfavorablethermodynamics that limit the extent of conversion to condensationproducts. The present invention has revealed that conducting thereaction with the condensation catalysts and at the temperatures andpressures described below overcomes these limitations and unexpectedlypromotes an immediate conversion of the condensation products tohydrocarbons, ketones and alcohols. The conversion, in turn, removes thecondensation products from the reaction, thereby overcoming thethermodynamic limitations of the system to allow additional condensationreactions to occur. Elevated temperature and/or pressure conditions alsoavoid excessive conversion of the oxygenates directly to theircorresponding hydrocarbons. The process also has the added benefit ofallowing for the condensation reactions, deoxygenation reactions and APRreactions to occur in a single reactor and under steady-stateequilibrium.

For any given reaction, the free energy change is indicative of thefavorability of the forward reaction. The more negative the free energychange, the more favorable the reaction. As a result, reactionsassociated with a highly negative change in free energy are generallyfavorable and have the potential to exhibit high conversions to reactionproducts. Conversely, reactions associated with positive changes in freeenergy are not favorable and are inherently limited in the extent towhich reactants are converted to products. As an illustration, FIG. 4shows the free energy changes associated with steps along the reactionpathway for converting acetone and hydrogen to a C₆ hydrocarbon(2-methylpentane) and water at 100° C. and 400° C. The known free energylevels of the stable intermediates derived along this pathway are shownwith a solid line. The first step in the reaction pathway is the aldolcondensation of two molecules of acetone to form one molecule ofdiacetone alcohol. The reaction at the lower temperature (100° C.) has afree energy change of −53 KJ/mole and is thermodynamically favored,while the reaction at the higher temperature (400° C.) is less favorabledue to a free energy change of −10 KJ/mole. The implication is that themaximum conversion of pure acetone to diacetone alcohol for this stepdecreases as the temperature is increased (greater than 99% theoreticalmaximal conversion at 100° C. at atmospheric pressure, to only 15% at400° C. at atmospheric pressure). Accordingly, the thermodynamicequilibrium limitation imposes an absolute limit to the amount ofdiacetone alcohol that may be produced under given conditions and in theabsence of other reactions. This is further illustrated in FIG. 5, whichprovides the equilibrium constants associated with the intermediatereaction products and the overall conversion for the reaction of 2 molesof acetone with 3 moles of hydrogen to form 1 mole of 2-methylpentaneand 2 moles of water. It can be seen that the equilibrium constant forthe conversion of acetone to diacetone alcohol decreases with increasingtemperature.

The present invention obviates this issue by immediately converting thecondensation product to a compound that provides a more favorablereaction environment. In the case above, by removing the diacetonealcohol from the reaction mixture through a dehydration reaction thatforms mesityl oxide, additional diacetone alcohol can be formed. Inparticular, the combination of a condensation and dehydration step toprovide mesityl oxide and water from acetone provides a slightly morefavorable reaction environment. As illustrated in FIG. 5, the conversionof acetone to mesityl oxide and water is slightly more favorable at thehigher temperatures.

The total reaction system pressure also has a beneficial effect on themaximal theoretical extent to which reactant may form a product.Considering the condensation reaction example above, the conversion ofacetone to diacetone alcohol is limited to 15% at 400° C. at atmosphericpressure with pure acetone feed. By increasing the system pressure to600 psi gauge pressure, the equilibrium conversion shifts so that up to76% conversion may be achieved at the same temperature. For reactionsexhibiting a net decrease in the number of moles of product as comparedto the moles of reactant, an increase in system pressure (with all otherconditions held constant) will act to increase the equilibrium productconversion. For the overall conversion of ketones to hydrocarbons, thereis typically a net decrease in the moles of product compared to themoles of reactant, thus higher reaction pressures would lead to higherpotential equilibrium conversions.

The present invention strikes a balance with the above thermodynamiclimitations by operating with condensation catalysts and at temperatureand pressure conditions that offset any reduction in the production ofcondensation products with an increase in the conversion to otherdownstream products. The kinetics of the entire system is also morefavorable such that products may be produced continuously and at a moredesirable rate. In terms of scaled-up production, after start-up, thereactor systems may be process controlled, and the reactions couldproceed at steady-state equilibrium.

Oxygenates

The C₄₊ compounds are derived from oxygenates. As used herein,“oxygenates” generically refers to hydrocarbon compounds having 1 ormore carbon atoms and between 1 and 3 oxygen atoms (referred to hereinas C₁₊O₁₋₃ hydrocarbons), such as alcohols, ketones, aldehydes, furans,hydroxy carboxylic acids, carboxylic acids, diols and triols.Preferably, the oxygenates have from 1 to 6 carbon atoms, or 2 to 6carbon atoms, or 3 to 6 carbon atoms. Alcohols may include, withoutlimitation, primary, secondary, linear, branched or cyclic C₁₊ alcohols,such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, butylalcohol, isobutyl alcohol, butanol, pentanol, cyclopentanol, hexanol,cyclohexanol, 2-methyl-cyclopentanonol, heptanol, octanol, nonanol,decanol, undecanol, dodecanol, and isomers thereof. The ketones mayinclude, without limitation, hydroxyketones, cyclic ketones, diketones,acetone, propanone, 2-oxopropanal, butanone, butane-2,3-dione,3-hydroxybutan-2-one, pentanone, cyclopentanone, pentane-2,3-dione,pentane-2,4-dione, hexanone, cyclohexanone, 2-methyl-cyclopentanone,heptanone, octanone, nonanone, decanone, undecanone, dodecanone,methylglyoxal, butanedione, pentanedione, diketohexane, and isomersthereof. The aldehydes may include, without limitation,hydroxyaldehydes, acetaldehyde, propionaldehyde, butyraldehyde,pentanal, hexanal, heptanal, octanal, nonal, decanal, undecanal,dodecanal, and isomers thereof. The carboxylic acids may include,without limitation, formic acid, acetic acid, propionic acid, butanoicacid, pentanoic acid, hexanoic acid, heptanoic acid, isomers andderivatives thereof, including hydroxylated derivatives, such as2-hydroxybutanoic acid and lactic acid. The diols may include, withoutlimitation, ethylene glycol, propylene glycol, 1,3-propanediol,butanediol, pentanediol, hexanediol, heptanediol, octanediol,nonanediol, decanediol, undecanediol, dodecanediol, and isomers thereof.The triols may include, without limitation, glycerol, 1,1,1tris(hydroxymethyl)-ethane (trimethylolethane), trimethylolpropane,hexanetriol, and isomers thereof. Furans and furfurals include, withoutlimitation, furan, tetrahydrofuran, dihydrofuran, 2-furan methanol,2-methyl-tetrahydrofuran, 2,5-dimethyl-tetrahydrofuran, 2-methyl furan,2-ethyl-tetrahydrofuran, 2-ethyl furan, hydroxylmethylfurfural,3-hydroxytetrahydrofuran, tetrahydro-3-furanol, 2,5-dimethyl furan,5-hydroxymethyl-2(5H)-furanone,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydro-2-furoic acid,dihydro-5-(hydroxymethyl)-2(3H)-furanone, tetrahydrofurfuryl alcohol,1-(2-furyl)ethanol, hydroxymethyltetrahydrofurfural, and isomersthereof.

The oxygenates may originate from any source, but are preferably derivedfrom biomass. As used herein, the term “biomass” refers to, withoutlimitation, organic materials produced by plants (such as leaves, roots,seeds and stalks), and microbial and animal metabolic wastes. Commonsources of biomass include: (1) agricultural wastes, such as cornstalks, straw, seed hulls, sugarcane leavings, bagasse, nutshells, andmanure from cattle, poultry, and hogs; (2) wood materials, such as woodor bark, sawdust, timber slash, and mill scrap; (3) municipal waste,such as waste paper and yard clippings; and (4) energy crops, such aspoplars, willows, switch grass, alfalfa, prairie bluestream, corn,soybean, and the like. The term also refers to the primary buildingblocks of the above, namely, saccharides, lignin, cellulosics,hemicellulose and starches, among others.

Oxygenates from biomass may be produced by any known method. Suchmethods include fermentation technologies using enzymes ormicroorganisms, Fischer-Tropsch reactions to produce C₂₋₁₀ alphaalcohols, and pyrolysis technologies to produce alcohols from oil, amongothers. In one embodiment, the oxygenates are produced using catalyticreforming technologies, such as the BioForming™ technology developed byVirent Energy Systems, Inc. (Madison, Wis.).

Oxygenated Hydrocarbons

In one embodiment, the oxygenates are derived from the catalyticreforming of oxygenated hydrocarbons. The oxygenated hydrocarbons may beany water-soluble oxygenated hydrocarbon having one or more carbon atomsand at least one oxygen atom (referred to herein as C₁₊O₁₊hydrocarbons). Preferably, the oxygenated hydrocarbon has 2 to 12 carbonatoms (C₁₋₁₂O₁₋₁₁ hydrocarbon), and more preferably 2 to 6 carbon atoms(C₁₋₆O₁₋₆ hydrocarbon). The oxygenated hydrocarbon may also have anoxygen-to-carbon ratio ranging from 0.5:1 to 1.5:1, including ratios of0.75:1.0, 1.0:1.0, 1.25:1.0, 1.5:1.0, and other ratios between. In oneexample, the oxygenated hydrocarbon has an oxygen-to-carbon ratio of1:1. Nonlimiting examples of preferred water-soluble oxygenatedhydrocarbons include monosaccharides, disaccharides, polysaccharides,sugar, sugar alcohols, alditols, ethanediol, ethanedione, acetic acid,propanol, propanediol, propionic acid, glycerol, glyceraldehyde,dihydroxyacetone, lactic acid, pyruvic acid, malonic acid, butanediols,butanoic acid, aldotetroses, tautaric acid, aldopentoses, aldohexoses,ketotetroses, ketopentoses, ketohexoses, alditols, hemicelluloses,cellulosic derivatives, lignocellulosic derivatives, starches, polyolsand the like. Preferably, the oxygenated hydrocarbon includes sugar,sugar alcohols, saccharides and other polyhydric alcohols. Morepreferably, the oxygenated hydrocarbon is a sugar, such as glucose,fructose, sucrose, maltose, lactose, mannose or xylose, or a sugaralcohol, such as arabitol, erythritol, glycerol, isomalt, lactitol,malitol, mannitol, sorbitol, xylitol, ribitol, or glycol.

Oxygenated hydrocarbons shall also refer to and include alcohols derivedby hydrogenation or hydrogenolysis of any of the foregoing. In certainembodiments, it may be preferable to convert the starting oxygenatedhydrocarbon to another oxygenated hydrocarbon form that can be morereadily converted to the desired oxygenates (e.g., primary, secondary,tertiary or polyhydric alcohols). For instance, some sugars may notconvert as efficiently to oxygenates as compared to their correspondingsugar alcohol derivatives. It may therefore be desirable to convert thestarting material, such as a sugar, furfural, carboxylic acid, ketone,or furan, into its corresponding alcohol derivative, such as byhydrogenation, or to smaller alcohol molecules, such as byhydrogenolysis.

Various processes are known for hydrogenating sugars, furfurals,carboxylic acids, ketones, and furans to their corresponding alcoholform, including those disclosed by: B. S. Kwak et al. (WO2006/093364A1and WO 2005/021475A1), involving the preparation of sugar alditols frommonosaccharides by hydrogenation over a ruthenium catalyst; and Elliotet al. (U.S. Pat. Nos. 6,253,797 and 6,570,043), disclosing the use of anickel and rhenium free ruthenium catalyst on a more than 75% rutiletitania support to convert sugars to sugar alcohols, all incorporatedherein by reference. Other suitable ruthenium catalysts are described byArndt et al. in published U.S. patent application 2006/0009661 (filedDec. 3, 2003), and Arena in U.S. Pat. No. 4,380,679 (filed Apr. 12,1982), U.S. Pat. No. 4,380,680 (filed May 21, 1982), U.S. Pat. No.4,503,274 (filed Aug. 8, 1983), U.S. Pat. No. 4,382,150 (filed Jan. 19,1982), and U.S. Pat. No. 4,487,980 (filed Apr. 29, 1983), allincorporated herein by reference. The hydrogenation catalyst generallyincludes Cu, Re, Ni, Fe, Co, Ru, Pd, Rh, Pt, Os, Ir, and alloys orcombinations thereof, either alone or with promoters such as W, Mo, Au,Ag, Cr, Zn, Mn, Sn, B, P, Bi, and alloys or combinations thereof. Thehydrogenation catalyst may also include any one of the supports furtherdescribed below, and depending on the desired functionality of thecatalyst. Other effective hydrogenation catalyst materials includeeither supported nickel or ruthenium modified with rhenium. In general,the hydrogenation reaction is carried out at hydrogenation temperaturesof between about 80° C. to 250° C., and hydrogenation pressures in therange of about 100 psig to 2000 psig. The hydrogen used in the reactionmay include in situ generated H₂, external H₂, recycled H₂, or acombination thereof.

The hydrogenation catalyst may also include a supported Group VIII metalcatalyst and a metal sponge material, such as a sponge nickel catalyst.Activated sponge nickel catalysts (e.g., Raney nickel) are a well-knownclass of materials effective for various hydrogenation reactions. Onetype of sponge nickel catalyst is the type A7063 catalyst available fromActivated Metals and Chemicals, Inc., Sevierville, Tenn. The type A7063catalyst is a molybdenum promoted catalyst, typically containingapproximately 1.5% molybdenum and 85% nickel. The use of the spongenickel catalyst with a feedstock comprising xylose and dextrose isdescribed by M. L. Cunningham et al. in U.S. Pat. No. 6,498,248, filedSep. 9, 1999, incorporated herein by reference. The use of a Raneynickel catalyst with hydrolyzed corn starch is also described in U.S.Pat. No. 4,694,113, filed Jun. 4, 1986, and incorporated herein byreference.

The preparation of suitable Raney nickel hydrogenation catalysts isdescribed by A. Yoshino et al. in published U.S. patent application2004/0143024, filed Nov. 7, 2003, incorporated herein by reference. TheRaney nickel catalyst may be prepared by treating an alloy ofapproximately equal amounts by weight of nickel and aluminum with anaqueous alkali solution, e.g., containing about 25 wt. % of sodiumhydroxide. The aluminum is selectively dissolved by the aqueous alkalisolution leaving particles having a sponge construction and composedpredominantly of nickel with a minor amount of aluminum. Promotermetals, such as molybdenum or chromium, may be also included in theinitial alloy in an amount such that about 1-2 wt. % remains in thesponge nickel catalyst.

In another embodiment, the hydrogenation catalyst is prepared byimpregnating a suitable support material with a solution of ruthenium(III) nitrosylnitrate, ruthenium (III) nitrosylnitrate, or ruthenium(III) chloride in water to form a solid that is then dried for 13 hoursat 120° C. in a rotary ball oven (residual water content is less than 1%by weight). The solid is then reduced at atmospheric pressure in ahydrogen stream at 300° C. (uncalcined) or 400° C. (calcined) in therotary ball furnace for 4 hours. After cooling and rendering inert withnitrogen, the catalyst may then be passivated by passing over 5% byvolume of oxygen in nitrogen for a period of 120 minutes.

In yet another embodiment, the hydrogenation reaction is performed usinga catalyst comprising a nickel-rhenium catalyst or a tungsten-modifiednickel catalyst. One example of a suitable hydrogenation catalyst is thecarbon-supported nickel-rhenium catalyst composition disclosed by Werpyet al. in U.S. Pat. No. 7,038,094, filed Sep. 30, 2003, and incorporatedherein by reference.

In other embodiments, it may also be desirable to convert the startingoxygenated hydrocarbon, such as a sugar, sugar alcohol or otherpolyhydric alcohol, to a smaller molecule that can be more readilyconverted to the desired oxygenates, such as by hydrogenolysis. Suchsmaller molecules may include primary, secondary, tertiary or polyhydricalcohols having less carbon atoms than the originating oxygenatedhydrocarbon. Various processes are known for such hydrogenolysisreactions, including those disclosed by: Werpy et al. in U.S. Pat. No.6,479,713 (filed Oct. 23, 2001), U.S. Pat. No. 6,677,385 (filed Aug. 6,2002), U.S. Pat. No. 6,6841,085 (filed Oct. 23, 2001) and U.S. Pat. No.7,083,094 (filed Sep. 30, 2003), all incorporated herein by referenceand describing the hydrogenolysis of 5 and 6 carbon sugars and sugaralcohols to propylene glycol, ethylene glycol and glycerol using arhenium-containing multi-metallic catalyst. Other systems include thosedescribed by Arena in U.S. Pat. No. 4,401,823 (filed May 18, 1981)directed to the use of a carbonaceous pyropolymer catalyst containingtransition metals (such as chromium, molybdenum, tungsten, rhenium,manganese, copper, cadmium) or Group VIII metals (such as iron, cobalt,nickel, platinum, palladium, rhodium, ruthenium, iridium and osmium) toproduce alcohols, acids, ketones, and ethers from polyhydroxylatedcompounds, such as sugars and sugar alcohols, and U.S. Pat. No.4,496,780 (filed Jun. 22, 1983) directed to the use of a catalyst systemhaving a Group VIII noble metal on a solid support with an alkalineearth metal oxide to produce glycerol, ethylene glycol and1,2-propanediol from carbohydrates, each incorporated herein byreference. Another system includes that described by Dubeck et al. inU.S. Pat. No. 4,476,331 (filed Sep. 6, 1983) directed to the use of asulfide-modified ruthenium catalyst to produce ethylene glycol andpropylene glycol from larger polyhydric alcohols, such as sorbitol, alsoincorporated herein by reference. Other systems include those describedby Saxena et al., “Effect of Catalyst Constituents on (Ni, Mo andCu)/Kieselguhr-Catalyzed Sucrose Hydrogenolysis,” Ind. Eng. Chem. Res.44, 1466-1473 (2005), describing the use of Ni, W, and Cu on akieselguhr support, incorporated herein by reference.

In one embodiment, the hydrogenolysis catalyst includes Cr, Mo, W, Re,Mn, Cu, Cd, Fe, Co, Ni, Pt, Pd, Rh, Ru, Ir, or Os, and alloys orcombinations thereof, either alone or with promoters such as Au, Ag, Cr,Zn, Mn, Sn, Bi, B, O and alloys or combinations thereof. Other effectivehydrogenolysis catalyst materials may include the above metals combinedwith an alkaline earth metal oxide or adhered to catalytically activesupport, such as kieselguhr, or any one of the supports furtherdescribed below.

The process conditions for carrying out the hydrogenolysis reaction willvary depending on the type of feedstock and desired products. Ingeneral, the hydrogenolysis reaction is conducted at temperatures of atleast 110° C., or between 110° C. and 300° C., or between 170° C. and240° C. The reaction should also be conducted under basic conditions,preferably at a pH of about 8 to about 13, or at a pH of about 10 toabout 12. The reaction should also be conducted at pressures of betweenabout 10 psig and 2400 psig, or between about 250 psig and 2000 psig, orbetween about 700 psig and 1600 psig. The hydrogen used in the reactionmay include in situ generated H₂, external H₂, recycled H₂, or acombination thereof.

Production of Oxygenates

The oxygenates are prepared by reacting an aqueous feedstock solutioncontaining water and the water soluble oxygenated hydrocarbons withhydrogen over a catalytic material to produce the desired oxygenates.Preferably, the hydrogen is generated in situ using aqueous phasereforming (in situ generated H₂ or APR H₂), or a combination of APR H₂,external H₂ or recycled H₂, or just simply external H₂ or recycled H₂.The term “external H₂” refers to hydrogen that does not originate fromthe feedstock solution, but is added to the reactor system from anexternal source. The term “recycled H₂” refers to unconsumed hydrogenthat originates from the feedstock solution, and which is collected andthen recycled back into the reactor system for further use. External H₂and recycled H₂ may also be referred to collectively or individually as“supplemental H₂.” In general, supplemental H₂ may be added for purposesof supplementing the APR hydrogen, or to substitute the inclusion of anAPR hydrogen production step, or to increase the reaction pressurewithin the system, or to increase the molar ratio of hydrogen to carbonand/or oxygen in order to enhance the production yield of certainreaction product types, such as ketones and alcohols.

In processes utilizing APR H₂, the oxygenates are prepared bycatalytically reacting a portion of the aqueous feedstock solutioncontaining water and the water soluble oxygenated hydrocarbons in thepresence of an APR catalyst at a reforming temperature and reformingpressure to produce the APR H₂, and catalytically reacting the APR H₂(and recycled H₂ and/or external H₂) with a portion of the feedstocksolution in the presence of a deoxygenation catalyst at a deoxygenationtemperature and deoxygenation pressure to produce the desiredoxygenates. In systems utilizing recycled H₂ or external H₂ as ahydrogen source, the oxygenates are simply prepared by catalyticallyreacting the recycled H₂ and/or external H₂ with the feedstock solutionin the presence of the deoxygenation catalyst at the deoxygenationtemperatures and pressures. In each of the above, the oxygenates mayalso include recycled oxygenates (recycled C₁₊O₁₋₃ hydrocarbons). Unlessotherwise indicated, any discussions of APR catalysts and deoxygenationcatalysts are non-limiting examples of suitable catalytic materials.

The deoxygenation catalyst is preferably a heterogeneous catalyst havingone or more materials capable of catalyzing a reaction between hydrogenand the oxygenated hydrocarbon to remove one or more of the oxygen atomsfrom the oxygenated hydrocarbon to produce alcohols, ketones, aldehydes,furans, carboxylic acids, hydroxy carboxylic acids, diols and triols. Ingeneral, the materials will be adhered to a support and may include,without limitation, Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd, Ni, W, Os, Mo,Ag, Au, alloys and combinations thereof. The deoxygenation catalyst mayinclude these elements alone or in combination with one or more Mn, Cr,Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga,In, Tl, and combinations thereof. In one embodiment, the deoxygenationcatalyst includes Pt, Ru, Cu, Re, Co, Fe, Ni, W or Mo. In yet anotherembodiment, the deoxygenation catalyst includes Fe or Re and at leastone transition metal selected from Ir, Ni, Pd, P, Rh, and Ru. In anotherembodiment, the catalyst includes Fe, Re and at least Cu or one GroupVIIIB transition metal. The support may be any one of the supportsfurther described below, including a nitride, carbon, silica, alumina,zirconia, titania, vanadia, ceria, zinc oxide, chromia, boron nitride,heteropolyacids, kieselguihr, hydroxyapatite, and mixtures thereof. Thedeoxygenation catalyst may also be atomically identical to the APRcatalyst or the condensation catalyst.

The deoxygenation catalyst may also be a bi-functional catalyst. Forexample, acidic supports (e.g., supports having low isoelectric points)are able to catalyze dehydration reactions of oxygenated compounds,followed by hydrogenation reactions on metallic catalyst sites in thepresence of H₂, again leading to carbon atoms that are not bonded tooxygen atoms. The bi-functional dehydration/hydrogenation pathwayconsumes H₂ and leads to the subsequent formation of various polyols,diols, ketones, aldehydes, alcohols and cyclic ethers, such as furansand pyrans. Catalyst examples include tungstated zirconia, titaniazirconia, sulfated zirconia, acidic alumina, silica-alumina, zeolitesand heteropolyacid supports. Heteropolyacids are a class of solid-phaseacids exemplified by such species as H_(3+x)PMo_(12-x)V_(x)O₄₀,H₄SiW₁₂O₄₀, H₃PW₁₂O₄₀, and H₆P2W₁₈O₆₂. Heteropolyacids are solid-phaseacids having a well-defined local structure, the most common of which isthe tungsten-based Keggin structure.

Loading of the first element (i.e., Cu, Re, Fe, Ru, Ir, Co, Rh, Pt, Pd,Ni, W, Os, Mo, Ag, Au, alloys and combinations thereof) is in the rangeof 0.25 wt % to 25 wt % on carbon, with weight percentages of 0.10% and0.05% increments between, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%,5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio ofthe second element (i.e., Mn, Cr, Mo, W, V, Nb, Ta, Ti, Zr, Y, La, Sc,Zn, Cd, Ag, Au, Sn, Ge, P, Al, Ga, In, Tl, and combinations thereof) isin the range of 0.25-to-1 to 10-to-1, including any ratios between, suchas 0.50, 1.00, 2.50, 5.00, and 7.50-to-1. If the catalyst is adhered toa support, the combination of the catalyst and the support is from 0.25wt % to 10 wt % of the primary element.

To produce oxygenates, the oxygenated hydrocarbon is combined with waterto provide an aqueous feedstock solution having a concentrationeffective for causing the formation of the desired reaction products.The water-to-carbon ratio on a molar basis is preferably from about0.5:1 to about 100:1, including ratios such as 1:1, 2:1, 3:1, 4:1, 5:1,6:1, 7:1, 8:1, 9:1, 10:1, 15:1, 25:1, 50:1 75:1, 100:1, and any ratiosthere-between. The feedstock solution may also be characterized as asolution having at least 1.0 weight percent (wt %) of the total solutionas an oxygenated hydrocarbon. For instance, the solution may include oneor more oxygenated hydrocarbons, with the total concentration of theoxygenated hydrocarbons in the solution being at least about 1%, 5%,10%, 20%, 30%, 40%, 50%, 60%, 70%, 80% or greater by weight, includingany percentages between, and depending on the oxygenated hydrocarbonsused. In one embodiment, the feedstock solution includes at least about10%, 20%, 30%, 40%, 50%, or 60% of a sugar, such as glucose, fructose,sucrose or xylose, or a sugar alcohol, such as sorbitol, mannitol,glycerol or xylitol, by weight. Water-to-carbon ratios and percentagesoutside of the above stated ranges are also included. Preferably thebalance of the feedstock solution is water. In some embodiments, thefeedstock solution consists essentially of water, one or more oxygenatedhydrocarbons and, optionally, one or more feedstock modifiers describedherein, such as alkali or hydroxides of alkali or alkali earth salts oracids. The feedstock solution may also include recycled oxygenatedhydrocarbons recycled from the reactor system. The feedstock solutionmay also contain negligible amounts of hydrogen, preferably less thanabout 1.5 mole of hydrogen per mole of feedstock. In the preferredembodiments, hydrogen is not added to the feedstock solution.

The feedstock solution is reacted with hydrogen in the presence of thedeoxygenation catalyst at deoxygenation temperature and pressureconditions, and weight hourly space velocity, effective to produce thedesired oxygenates. The specific oxygenates produced will depend onvarious factors, including the feedstock solution, reaction temperature,reaction pressure, water concentration, hydrogen concentration, thereactivity of the catalyst, and the flow rate of the feedstock solutionas it affects the space velocity (the mass/volume of reactant per unitof catalyst per unit of time), gas hourly space velocity (GHSV), andweight hourly space velocity (WHSV). For example, an increase in flowrate, and thereby a reduction of feedstock exposure to the catalystsover time, will limit the extent of the reactions which may occur,thereby causing increased yield for higher level diols and triols, witha reduction in ketone and alcohol yields.

The deoxygenation temperature and pressure are preferably selected tomaintain at least a portion of the feedstock in the liquid phase at thereactor inlet. It is recognized, however, that temperature and pressureconditions may also be selected to more favorably produce the desiredproducts in the vapor-phase. In general, the reaction should beconducted at process conditions wherein the thermodynamics of theproposed reaction are favorable. For instance, the minimum pressurerequired to maintain a portion of the feedstock in the liquid phase willlikely vary with the reaction temperature. As temperatures increase,higher pressures will generally be required to maintain the feedstock inthe liquid phase, if desired. Pressures above that required to maintainthe feedstock in the liquid phase (i.e., vapor-phase) are also suitableoperating conditions.

In condensed phase liquid reactions, the pressure within the reactormust be sufficient to maintain the reactants in the condensed liquidphase at the reactor inlet. For liquid phase reactions, the reactiontemperature may be from about 80° C. to 300° C., and the reactionpressure from about 72 psig to 1300 psig. In one embodiment, thereaction temperature is between about 120° C. and 300° C., or betweenabout 200° C. and 280° C., or between about 220° C. and 260° C., and thereaction pressure is preferably between about 72 and 1200 psig, orbetween about 145 and 1200 psig, or between about 200 and 725 psig, orbetween about 365 and 700 psig, or between about 600 and 650 psig.

For vapor phase reactions, the reaction should be carried out at atemperature where the vapor pressure of the oxygenated hydrocarbon is atleast about 0.1 atm (and preferably a good deal higher), and thethermodynamics of the reaction are favorable. This temperature will varydepending upon the specific oxygenated hydrocarbon compound used, but isgenerally in the range of from about 100° C. to 600° C. for vapor phasereactions. Preferably, the reaction temperature is between about 120° C.and about 300° C., or between about 200° C. and about 280° C., orbetween about 220° C. and about 260° C.

In another embodiment, the deoxygenation temperature is between about100° C. and 400° C., or between about 120° C. and 300° C., or betweenabout 200° C. and 280° C., and the reaction pressure is preferablybetween about 72 and 1300 psig, or between about 72 and 1200 psig, orbetween about 200 and 725 psig, or between about 365 and 700 psig.

A condensed liquid phase method may also be performed using a modifierthat increases the activity and/or stability of the catalyst system. Itis preferred that the water and the oxygenated hydrocarbon are reactedat a suitable pH of from about 1.0 to about 10.0, including pH values inincrements of 0.1 and 0.05 between, and more preferably at a pH of fromabout 4.0 to about 10.0. Generally, the modifier is added to thefeedstock solution in an amount ranging from about 0.1% to about 10% byweight as compared to the total weight of the catalyst system used,although amounts outside this range are included within the presentinvention.

In general, the reaction should be conducted under conditions where theresidence time of the feedstock solution over the catalyst isappropriate to generate the desired products. For example, the WHSV forthe reaction may be at least about 0.1 gram of oxygenated hydrocarbonper gram of catalyst per hour, and more preferably the WHSV is about 0.1to 40.0 g/g hr, including a WHSV of about 0.25, 0.5, 0.75, 1.0, 1.0,1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4,2.5, 2.6, 2.7, 2.8, 2.9, 3.0, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8,3.9, 4.0, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5.0, 6, 7, 8, 9,10, 11, 12, 13, 14, 15, 20, 25, 30, 35, 40 g/g hr.

The hydrogen used in the deoxygenation reaction is preferably in-situgenerated H₂, but may also be external or recycled H₂. When present, theamount of external H₂ is preferably provided sparingly. Most preferably,the amount of external H₂ is provided in amounts that provide less thanone hydrogen atom per oxygen atom in all of the oxygenated hydrocarbonsin the feedstock stream prior to contacting the deoxygenation catalyst.For example, the molar ratio between the external H₂ and the totalwater-soluble oxygenated hydrocarbons in the feedstock solution ispreferably selected to provide no more than one hydrogen atom per oxygenatom in the oxygenated hydrocarbon. The molar ratio of the oxygenatedhydrocarbons in the feedstock to the external H₂ introduced to thefeedstock is also preferably not more than 1:1, or more preferably up to2:1, 3:1, 5:1, 10:1, 20:1 or greater (including 4:1, 6:1, 7:1, 8:1, 9:1,11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1 and 19:1). The amount(moles) of external H₂ introduced to the feedstock is between 0-100%,0-95%, 0-90%, 0-85%, 0-80%, 0-75%, 0-70%, 0-65%, 0-60%, 0-55%, 0-50%,0-45%, 0-40%, 0-35%, 0-30%, 0-25%, 0-20%, 0-15%, 0-10%, 0-5%, 0-2%, or0-1% of the total number of moles of the oxygenated hydrocarbon(s) inthe feedstock, including all intervals between. When the feedstocksolution, or any portion thereof, is reacted with APR hydrogen andexternal H₂, the molar ratio of APR hydrogen to external H₂ is at least1:20; 1:15, 1:10, 1:5; 1:3, 1:2, 1:1, 2:1, 3:1, 5:1, 10:1, 15:1, 20:1,and ratios between (including 4:1, 6:1, 7:1, 8:1, 9:1, 11:1, 12:1, 13:1,14:1, 15:1, 16:1, 17:1, 18:1 and 19:1, and vice-versa). Preferably, theoxygenated hydrocarbon is reacted with H₂ in the presence of aninsignificantly effective amount of external H₂.

The amount of external H₂ (or supplemental H₂) added may be calculatedby considering the concentration of the oxygenated hydrocarbons in thefeedstock solution. Preferably, the amount of supplemental H₂ addedshould provide a molar ratio of oxygen atoms in the oxygenatedhydrocarbons to moles of hydrogen atoms (i.e., 2 oxygen atoms permolecule of H₂ gas) of less than or equal to 1.0. For example, where thefeedstock is an aqueous solution consisting of glycerol (3 oxygenatoms), the amount of supplemental H₂ added to the feedstock ispreferably not more than about 1.5 moles of H₂ per mole of glycerol(C₃H₈O₃), and preferably not more than about 1.25, 1.0, 0.75, 0.50 or0.25. In general, the amount of supplemental H₂ added is less than0.75-times, and more preferably not more than 0.67, 0.50, 0.33, 0.30,0.25, 0.20, 0.15, 0.10, 0.05, 0.01-times the amount of total H₂ (APR H₂and supplemental H₂) that would provide a 1:1 atomic ratio of oxygen tohydrogen atoms.

The amount of APR H₂ within a reactor may be identified or detected byany suitable method. APR H₂ may be determined based on the compositionof the product stream as a function of the composition of the feedstockstream, the catalyst composition(s) and the reaction conditions,independent of the actual reaction mechanism occurring within thefeedstock stream. The amount of APR H₂ may be calculated based on thecatalyst, reaction conditions (e.g., flow rate, temperature, pressure,etc.) and the contents of the feedstock and the reaction products. Forexample, the feedstock may be contacted with the APR catalyst (e.g.,platinum) to generate APR H₂ in situ and a first reaction product streamin the absence of a deoxygenation catalyst. The feedstock may also becontacted with both the APR catalyst and the deoxygenation catalyst toproduce a second reaction product stream. By comparing the compositionof the first reaction product stream and the second reaction productstream at comparable reaction conditions, one may identify the presenceof APR H₂ and calculate the amount of APR H₂ produced. For example, anincrease in the amount of oxygenated compounds with greater degrees ofhydrogenation in the reaction product compared to the feedstockcomponents may indicate the presence of APR H₂.

In-Situ Hydrogen Production

One advantage of the present invention is that it allows for theproduction and use of in-situ generated H₂. The APR H₂ is produced fromthe feedstock under aqueous phase reforming conditions using an aqueousphase reforming catalyst (APR catalyst). The APR catalyst is preferablya heterogeneous catalyst capable of catalyzing the reaction of water andoxygenated hydrocarbons to form H₂ under the conditions described below.In one embodiment, the APR catalyst includes a support and at least oneGroup VIIIB metal, Fe, Ru, Os, Ir, Co, Rh, Pt, Pd, Ni, alloys andcombinations thereof. The APR catalyst may also include at least oneadditional material from Group VIIIB, Group VIIB, Group VIB, Group VB,Group IVB, Group IIB, Group IB, Group IVA or Group VA metals, such asCu, B, Mn, Re, Cr, Mo, Bi, W, V, Nb, Ta, Ti, Zr, Y, La, Sc, Zn, Cd, Ag,Au, Sn, Ge, P, Al, Ga, In, Tl, alloys and combinations thereof. Thepreferred Group VIIB metal includes Re, Mn, or combinations thereof. Thepreferred Group VIB metal includes Cr, Mo, W, or a combination thereof.The preferred Group VIIIB metals include Pt, Rh, Ru, Pd, Ni, orcombinations thereof. The supports may include any one of the catalystsupports described below, depending on the desired activity of thecatalyst system.

The APR catalyst may also be atomically identical to the deoxygenationcatalyst or the condensation catalyst. For instance, the APR anddeoxygenation catalyst may include Pt alloyed or admixed with Ni, Ru,Cu, Fe, Rh, Re, alloys and combinations thereof. The APR catalyst anddeoxygenation catalyst may also include Ru alloyed or admixed with Ge,Bi, B, Ni, Sn, Cu, Fe, Rh, Pt, alloys and combinations thereof. The APRcatalyst may also include Ni alloyed or admixed with Sn, Ge, Bi, B, Cu,Re, Ru, Fe, alloys and combinations thereof.

Preferred loading of the primary Group VIIIB metal is in the range of0.25 wt % to 25 wt % on carbon, with weight percentages of 0.10% and0.05% increments between, such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%,5.00%, 10.00%, 12.50%, 15.00% and 20.00%. The preferred atomic ratio ofthe second material is in the range of 0.25-to-1 to 10-to-1, includingratios between, such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

A preferred catalyst composition is further achieved by the addition ofoxides of Group IIIB, and associated rare earth oxides. In such event,the preferred components would be oxides of either lanthanum or cerium.The preferred atomic ratio of the Group IIIB compounds to the primaryGroup VIIIB metal is in the range of 0.25-to-1 to 10-to-1, includingratios between, such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

Another preferred catalyst composition is one containing platinum andrhenium. The preferred atomic ratio of Pt to Re is in the range of0.25-to-1 to 10-to-1, including ratios there-between, such as 0.50,1.00, 2.50, 5.00, and 7.00-to-1. The preferred loading of the Pt is inthe range of 0.25 wt % to 5.0 wt %, with weight percentages of 0.10% and0.05% between, such as 0.35%, 0.45%, 0.75%, 1.10%, 1.15%, 2.00%, 2.50%,3.0%, and 4.0%.

Preferably, the APR catalyst and the deoxygenation catalyst are of thesame atomic formulation. The catalysts may also be of differentformulations. In such event, the preferred atomic ratio of the APRcatalyst to the deoxygenation catalyst is in the range of 5:1 to 1:5,such as, without limitation, 4.5:1, 4.0:1, 3.5:1, 3.0:1, 2.5:1, 2.0:1,1.5:1, 1:1, 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, and anyamounts between.

Similar to the deoxygenation reactions, the temperature and pressureconditions are preferably selected to maintain at least a portion of thefeedstock in the liquid phase at the reactor inlet. The reformingtemperature and pressure conditions may also be selected to morefavorably produce the desired products in the vapor-phase. In general,the APR reaction should be conducted at a temperature where thethermodynamics are favorable. For instance, the minimum pressurerequired to maintain a portion of the feedstock in the liquid phase willvary with the reaction temperature. As temperatures increase, higherpressures will generally be required to maintain the feedstock in theliquid phase. Any pressure above that required to maintain the feedstockin the liquid phase (i.e., vapor-phase) is also a suitable operatingpressure. For vapor phase reactions, the reaction should be conducted ata reforming temperature where the vapor pressure of the oxygenatedhydrocarbon compound is at least about 0.1 atm (and preferably a gooddeal higher), and the thermodynamics of the reaction are favorable. Thetemperature will vary depending upon the specific oxygenated hydrocarboncompound used, but is generally in the range of from about 100° C. to450° C., or from about 100° C. to 300° C., for reactions taking place inthe vapor phase. For liquid phase reactions, the reaction temperaturemay be from about 80° C. to 400° C., and the reaction pressure fromabout 72 psig to 1300 psig.

In one embodiment, the reaction temperature is between about 100° C. and400° C., or between about 120° C. and 300° C., or between about 200° C.and 280° C., or between about 150° C. and 270° C. The reaction pressureis preferably between about 72 and 1300 psig, or between about 72 and1200 psig, or between about 145 and 1200 psig, or between about 200 and725 psig, or between about 365 and 700 psig, or between about 600 and650 psig.

A condensed liquid phase method may also be performed using a modifierthat increases the activity and/or stability of the APR catalyst system.It is preferred that the water and the oxygenated hydrocarbon arereacted at a suitable pH of from about 1.0 to 10.0, or at a pH of fromabout 4.0 to 10.0, including pH value increments of 0.1 and 0.05between. Generally, the modifier is added to the feedstock solution inan amount ranging from about 0.1% to about 10% by weight as compared tothe total weight of the catalyst system used, although amounts outsidethis range are included within the present invention.

Alkali or alkali earth salts may also be added to the feedstock solutionto optimize the proportion of hydrogen in the reaction products.Examples of suitable water-soluble salts include one or more selectedfrom the group consisting of an alkali or an alkali earth metalhydroxide, carbonate, nitrate, or chloride salt. For example, addingalkali (basic) salts to provide a pH of about pH 4.0 to about pH 10.0can improve hydrogen selectivity of reforming reactions.

The addition of acidic compounds may also provide increased selectivityto the desired reaction products in the hydrogenation reactionsdescribed below. It is preferred that the water-soluble acid is selectedfrom the group consisting of nitrate, phosphate, sulfate, chloridesalts, and mixtures thereof. If an acidic modifier is used, it ispreferred that it be present in an amount sufficient to lower the pH ofthe aqueous feed stream to a value between about pH 1.0 and about pH4.0. Lowering the pH of a feed stream in this manner may increase theproportion of oxygenates in the final reaction products.

In general, the reaction should be conducted under conditions where theresidence time of the feedstock solution over the APR catalyst isappropriate to generate an amount of APR hydrogen sufficient to reactwith a second portion of the feedstock solution over the deoxygenationcatalyst to provide the desired oxygenates. For example, the WHSV forthe reaction may be at least about 0.1 gram of oxygenated hydrocarbonper gram of APR catalyst, and preferably between about 1.0 to 40.0 gramsof oxygenated hydrocarbon per gram of APR catalyst, and more preferablybetween about 0.5 to 8.0 grams of oxygenated hydrocarbon per gram of APRcatalyst. In terms of scaled-up production, after start-up, the APRreactor system should be process controlled so that the reactionsproceed at steady-state equilibrium.

Condensation Step

The oxygenates produced are then converted into C₄₊ compounds bycondensation. Without being limited to any specific theories, it isbelieved that the acid condensation reactions generally consist of aseries of steps involving: (a) the dehydration of oxygenates to olefins;(b) oligomerization of the olefins; (c) cracking reactions; (d)cyclization of larger olefins to form aromatics; (e) paraffinisomerization; and (f) hydrogen-transfer reactions to form paraffins.Basic condensation reactions are believed to generally consist of aseries of steps involving: (1) aldol condensation to form aβ-hydroxyketone or β-hydroxyaldehyde; (2) dehydration of theβ-hydroxyketone or β-hydroxyaldehyde to form a conjugated enone; (3)hydrogenation of the conjugated enone to form a ketone or aldehyde,which may participate in further condensation reactions or conversion toan alcohol or hydrocarbon; and (4) hydrogenation of carbonyls toalcohols, or vice-versa. Acid-base condensation reactions are believedto generally involve any of the previous acidic and/or basic reactionssteps.

Production of the C₄₊ compounds occurs by condensation of the oxygenatesin the presence of a condensation catalyst. The condensation catalystwill generally be a catalyst capable of forming longer chain compoundsby linking two oxygen containing species through a new carbon-carbonbond, and converting the resulting compound to a hydrocarbon, alcohol orketone, such as an acid catalyst, basic catalyst or a multi-functionalcatalyst having both acid and base functionality. The condensationcatalyst may include, without limitation, carbides, nitrides, zirconia,alumina, silica, aluminosilicates, phosphates, zeolites, titaniumoxides, zinc oxides, vanadium oxides, lanthanum oxides, yttrium oxides,scandium oxides, magnesium oxides, cerium oxides, barium oxides, calciumoxides, hydroxides, heteropolyacids, inorganic acids, acid modifiedresins, base modified resins, and combinations thereof. The condensationcatalyst may include the above alone or in combination with a modifier,such as Ce, La, Y, Sc, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, andcombinations thereof. The condensation catalyst may also include ametal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd,Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinations thereof, toprovide a metal functionality. The condensation catalyst may also beatomically identical to the APR catalyst and/or the deoxygenationcatalyst.

The condensation catalyst may be self-supporting (i.e., the catalystdoes not need another material to serve as a support), or may require aseparate support suitable for suspending the catalyst in the reactantstream. One particularly beneficial support is silica, especially silicahaving a high surface area (greater than 100 square meters per gram),obtained by sol-gel synthesis, precipitation or fuming. In otherembodiments, particularly when the condensation catalyst is a powder,the catalyst system may include a binder to assist in forming thecatalyst into a desirable catalyst shape. Applicable forming processesinclude extrusion, pelletization, oil dropping, or other knownprocesses. Zinc oxide, alumina, and a peptizing agent may also be mixedtogether and extruded to produce a formed material. After drying, thismaterial is calcined at a temperature appropriate for formation of thecatalytically active phase, which usually requires temperatures inexcess of 450° C. Other catalyst supports may include those described infurther detail below.

Acid Catalysts

The acid condensation reaction is performed using acidic catalysts. Theacid catalysts may include, without limitation, aluminosilicates(zeolites), silica-alumina phosphates (SAPO), aluminum phosphates(ALPO), amorphous silica alumina, zirconia, sulfated zirconia,tungstated zirconia, tungsten carbide, molybdenum carbide, titania,acidic alumina, phosphated alumina, phosphated silica, sulfated carbons,phosphated carbons, acidic resins, heteropolyacids, inorganic acids, andcombinations thereof. In one embodiment, the catalyst may also include amodifier, such as Ce, Y, Sc, La, P, B, Bi, Li, Na, K, Rb, Cs, Mg, Ca,Sr, Ba, and combinations thereof. The catalyst may also be modified bythe addition of a metal, such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd,Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, to provide metal functionality, and/or sulfides and oxide ofTi, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si,Cu, Zn, Sn, Cd, P, and combinations thereof. Gallium has also been foundto be particularly useful as a promoter for the present process. Theacid catalyst may be homogenous, self-supporting or adhered to any oneof the supports further described below, including supports containingcarbon, silica, alumina, zirconia, titania, vanadia, ceria, nitride,boron nitride, heteropolyacids, alloys and mixtures thereof.

Ga, In, Zn, Fe, Mo, Ag, Au, Ni, P, Sc, Y, Ta, and lanthanides may alsobe exchanged onto zeolites to provide a zeolite catalyst havingactivity. The term “zeolite” as used herein refers not only tomicroporous crystalline aluminosilicate but also for microporouscrystalline metal-containing aluminosilicate structures, such asgalloaluminosilicates and gallosilicates. Metal functionality may beprovided by metals such as Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof.

Examples of suitable zeolite catalysts include ZSM-5, ZSM-11, ZSM-12,ZSM-22, ZSM-23, ZSM-35 and ZSM-48. Zeolite ZSM-5, and the conventionalpreparation thereof, is described in U.S. Pat. No. 3,702,886; Re. 29,948(highly siliceous ZSM-5); U.S. Pat. No. 4,100,262 and U.S. Pat. No.4,139,600, all incorporated herein by reference. Zeolite ZSM-11, and theconventional preparation thereof, is described in U.S. Pat. No.3,709,979, which is also incorporated herein by reference. ZeoliteZSM-12, and the conventional preparation thereof, is described in U.S.Pat. No. 3,832,449, incorporated herein by reference. Zeolite ZSM-23,and the conventional preparation thereof, is described in U.S. Pat. No.4,076,842, incorporated herein by reference. Zeolite ZSM-35, and theconventional preparation thereof, is described in U.S. Pat. No.4,016,245, incorporated herein by reference. Another preparation ofZSM-35 is described in U.S. Pat. No. 4,107,195, the disclosure of whichis incorporated herein by reference. ZSM-48, and the conventionalpreparation thereof, is taught by U.S. Pat. No. 4,375,573, incorporatedherein by reference. Other examples of zeolite catalysts are describedin U.S. Pat. No. 5,019,663 and U.S. Pat. No. 7,022,888, alsoincorporated herein by reference.

As described in U.S. Pat. No. 7,022,888, the acid catalyst may be abifunctional pentasil zeolite catalyst including at least one metallicelement from the group of Cu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga,In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys and combinationsthereof, or a modifier from the group of Ga, In, Zn, Fe, Mo, Au, Ag, Y,Sc, Ni, P, Ta, lanthanides, and combinations thereof. The zeolitepreferably has a strong acidic and dehydrogenation sites, and may beused with reactant streams containing and an oxygenated hydrocarbon at atemperature of below 500° C. The bifunctional pentasil zeolite may haveZSM-5, ZSM-8 or ZSM-11 type crystal structure consisting of a largenumber of 5-membered oxygen-rings, i.e., pentasil rings. The zeolitewith ZSM-5 type structure is a particularly preferred catalyst. Thebifunctional pentasil zeolite catalyst is preferably Ga and/orIn-modified ZSM-5 type zeolites such as Ga and/or In-impregnatedH-ZSM-5, Ga and/or In-exchanged H-ZSM-5, H-gallosilicate of ZSM-5 typestructure and H-galloaluminosilicate of ZSM-5 type structure. Thebifunctional ZSM-5 type pentasil zeolite may contain tetrahedralaluminum and/or gallium present in the zeolite framework or lattice andoctahedral gallium or indium. The octahedral sites are preferably notpresent in the zeolite framework but are present in the zeolite channelsin a close vicinity of the zeolitic protonic acid sites, which areattributed to the presence of tetrahedral aluminum and gallium in thezeolite. The tetrahedral or framework Al and/or Ga is believed to beresponsible for the acid function of zeolite and octahedral ornon-framework Ga and/or In is believed to be responsible for thedehydrogenation function of the zeolite.

In one embodiment, the condensation catalyst may be aH-galloaluminosilicate of ZSM-5 type bifunctional pentasil zeolitehaving framework (tetrahedral) Si/Al and Si/Ga mole ratio of about10-100 and 15-150, respectively, and non-framework (octahedral) Ga ofabout 0.5-5.0 wt. %. When these pentasil H-galloaluminosilicate zeolitesare used as a condensation catalyst, the density of strong acid sitescan be controlled by the framework Al/Si mole ratio: the higher theAl/Si ratio, the higher the density of strong acid sites. The highlydispersed non-framework gallium oxide species can be obtained by thedegalliation of the zeolite by its pretreatment with H₂ and steam. Thezeolite containing strong acid sites with high density and also highlydispersed non-framework gallium oxide species in close proximity of thezeolite acid site is preferred. The catalyst may optionally contain anybinder such as alumina, silica or clay material. The catalyst can beused in the form of pellets, extrudates and particles of differentshapes and sizes.

The acidic catalysts may include one or more zeolite structurescomprising cage-like structures of silica-alumina. Zeolites arecrystalline microporous materials with well-defined pore structure.Zeolites contain active sites, usually acid sites, which can begenerated in the zeolite framework. The strength and concentration ofthe active sites can be tailored for particular applications. Examplesof suitable zeolites for condensing secondary alcohols and alkanes maycomprise aluminosilicates optionally modified with cations, such as Ga,In, Zn, Mo, and mixtures of such cations, as described, for example, inU.S. Pat. No. 3,702,886, which is incorporated herein by reference. Asrecognized in the art, the structure of the particular zeolite orzeolites may be altered to provide different amounts of varioushydrocarbon species in the product mixture. Depending on the structureof the zeolite catalyst, the product mixture may contain various amountsof aromatic and cyclic hydrocarbons.

Alternatively, solid acid catalysts such as alumina modified withphosphates, chloride, silica, and other acidic oxides could be used inpracticing the present invention. Also, either sulfated zirconia ortungstated zirconia may provide the necessary acidity. Re and Pt/Recatalysts are also useful for promoting condensation of oxygenates toC₅₊ hydrocarbons and/or C₅₊ mono-oxygenates. The Re is sufficientlyacidic to promote acid-catalyzed condensation. Acidity may also be addedto activated carbon by the addition of either sulfates or phosphates.

Base Catalysts

The base condensation reaction is performed using a base catalyst. Thebase catalyst includes at least Li, Na, K, Cs, B, Rb, Mg, Ca, Sr, Si,Ba, Al, Zn, Ce, La, Y, Sc, Y, Zr, Ti, hydrotalcite, zinc-aluminate,phosphate, base-treated aluminosilicate zeolite, a basic resin, basicnitride, alloys or combinations thereof. The base catalyst may alsoinclude an oxide of Ti, Zr, V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In,Co, Ni, Si, Cu, Zn, Sn, Cd, Mg, P, Fe, and combinations thereof. In oneembodiment, the condensation catalyst further includes a metal, such asCu, Ag, Au, Pt, Ni, Fe, Co, Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr,Mo, W, Sn, Os, alloys and combinations thereof. Preferred Group IAmaterials include Li, Na, K, Cs and Rb. Preferred Group HA materialsinclude Mg, Ca, Sr and Ba. Preferred Group JIB materials include Zn andCd. Preferred Group IIIB materials include Y and La. Basic resinsinclude resins that exhibit basic functionality, such as Amberlyst. Thebase catalyst may be self-supporting or adhered to any one of thesupports further described below, including supports containing carbon,silica, alumina, zirconia, titania, vanadia, ceria, nitride, boronnitride, heteropolyacids, alloys and mixtures thereof.

The base catalyst may also include zeolites and other microporoussupports that contain Group IA compounds, such as Li, Na, K, Cs and Rb.Preferably, the Group IA material is present in an amount greater thanthat required to neutralize the acidic nature of the support. Thesematerials may be used in any combination, and also in combination withalumina or silica. A metal function may also be provided by the additionof group VIIIB metals, or Cu, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is derived from thecombination of MgO and Al₂O₃ to form a hydrotalcite material. Anotherpreferred material contains ZnO and Al₂O₃ in the form of a zincaluminate spinel. Yet another preferred material is a combination ofZnO, Al₂O₃, and CuO. Each of these materials may also contain anadditional metal function provided by a Group VIIIB metal, such as Pd orPt. In one embodiment, the base catalyst is a metal oxide containing Cu,Ni, Zn, V, Zr, or mixtures thereof. In another embodiment, the basecatalyst is a zinc aluminate metal containing Pt, Pd Cu, Ni, or mixturesthereof.

Preferred loading of the primary metal is in the range of 0.10 wt % to25 wt %, with weight percentages of 0.10% and 0.05% increments between,such as 1.00%, 1.10%, 1.15%, 2.00%, 2.50%, 5.00%, 10.00%, 12.50%, 15.00%and 20.00%. The preferred atomic ratio of the second metal, if any, isin the range of 0.25-to-1 to 10-to-1, including ratios there between,such as 0.50, 1.00, 2.50, 5.00, and 7.50-to-1.

Acid-Base Catalysts

The acid-base condensation reaction is performed using amulti-functional catalyst having both acid and base functionality. Theacid-base catalyst may include hydrotalcite, zinc-aluminate, phosphate,Li, Na, K, Cs, B, Rb, Mg, Si, Ca, Sr, Ba, Al, Ce, La, Sc, Y, Zr, Ti, Zn,Cr, and combinations thereof. In further embodiments, the acid-basecatalyst may also include one or more oxides from the group of Ti, Zr,V, Nb, Ta, Mo, Cr, W, Mn, Re, Al, Ga, In, Fe, Co, Ir, Ni, Si, Cu, Zn,Sn, Cd, P, and combinations thereof. The acid-base catalyst may alsoinclude a metal functionality provided by Cu, Ag, Au, Pt, Ni, Fe, Co,Ru, Zn, Cd, Ga, In, Rh, Pd, Ir, Re, Mn, Cr, Mo, W, Sn, Os, alloys orcombinations thereof. In one embodiment, the catalyst further includesZn, Cd or phosphate. In one embodiment, the condensation catalyst is ametal oxide containing Pd, Pt, Cu or Ni, and even more preferably analuminate or zirconium metal oxide containing Mg and Cu, Pt, Pd or Ni.The acid-base catalyst may also include a hydroxyapatite (HAP) combinedwith any one or more of the above metals. The acid-base catalyst may beself-supporting or adhered to any one of the supports further describedbelow, including supports containing carbon, silica, alumina, zirconia,titania, vanadia, ceria, nitride, boron nitride, heteropolyacids, alloysand mixtures thereof.

The condensation catalyst may also include zeolites and othermicroporous supports that contain Group IA compounds, such as Li, NA, K,Cs and Rb. Preferably, the Group IA material is present in an amountless than that required to neutralize the acidic nature of the support.A metal function may also be provided by the addition of group VIIIBmetals, or Cu, Ga, In, Zn or Sn.

In one embodiment, the condensation catalyst is derived from thecombination of MgO and Al₂O₃ to form a hydrotalcite material. Anotherpreferred material contains a combination of MgO and ZrO₂, or acombination of ZnO and Al₂O₃. Each of these materials may also containan additional metal function provided by copper or a Group VIIIB metal,such as Ni, Pd, Pt, or combinations of the foregoing.

If a Group IIB, VIB, VIIB, VIIIB, IIA or IVA metal is included, theloading of the metal is in the range of 0.10 wt % to 10 wt %, withweight percentages of 0.10% and 0.05% increments between, such as 1.00%,1.10%, 1.15%, 2.00%, 2.50%, 5.00% and 7.50%, etc. If a second metal isincluded, the preferred atomic ratio of the second metal is in the rangeof 0.25-to-1 to 5-to-1, including ratios there between, such as 0.50,1.00, 2.50 and 5.00-to-1.

Condensation Reactions

The specific C₄₊ compounds produced will depend on various factors,including, without limitation, the type of oxygenates in the reactantstream, condensation temperature, condensation pressure, the reactivityof the catalyst, and the flow rate of the reactant stream as it affectsthe space velocity, GHSV and WHSV. Preferably, the reactant stream iscontacted with the condensation catalyst at a WHSV that is appropriateto produce the desired hydrocarbon products. The WHSV is preferably atleast about 0.1 grams of oxygenate in the reactant stream per hour, morepreferably the WHSV is between about 0.1 to 40.0 g/g hr, including aWHSV of about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25,30, 35 g/g hr, and increments between.

In general, the condensation reaction should be carried out at atemperature at which the thermodynamics of the proposed reaction arefavorable. For condensed phase liquid reactions, the pressure within thereactor must be sufficient to maintain at least a portion of thereactants in the condensed liquid phase at the reactor inlet. For vaporphase reactions, the reaction should be carried out at a temperaturewhere the vapor pressure of the oxygenates is at least about 0.1 atm(and preferably a good deal higher), and the thermodynamics of thereaction are favorable. The condensation temperature will vary dependingupon the specific oxygenate used, but is generally in the range of fromabout 80° C. to 500° C. for reactions taking place in the vapor phase,and more preferably from about 125° C. to 450° C. For liquid phasereactions, the condensation temperature may be from about 80° C. to 500°C., and the condensation pressure from about 0 psig to 1200 psig.Preferably, the condensation temperature is between about 125° C. and300° C., or between about 125° C. and 250° C., or between about 250° C.and 425° C. The reaction pressure is preferably at least about 0.1 atm,or between about 0 and 1200 psig, or between about 0 and 1000 psig, orbetween about 0 and 700 psig.

Varying the factors above, as well as others, will generally result in amodification to the specific composition and yields of the C₄₊compounds. For example, varying the temperature and/or pressure of thereactor system, or the particular catalyst formulations, may result inthe production of C₄₊ alcohols and/or ketones instead of C₄₊hydrocarbons. The C₄₊ hydrocarbon product may also contain a variety ofolefins, and alkanes of various sizes (typically branched alkanes).Depending upon the condensation catalyst used, the hydrocarbon productmay also include aromatic and cyclic hydrocarbon compounds. The C₄₊hydrocarbon product may also contain undesirably high levels of olefins,which may lead to coking or deposits in combustion engines, or otherundesirable hydrocarbon products. In such event, the hydrocarbonmolecules produced may be optionally hydrogenated to reduce the ketonesto alcohols and hydrocarbons, while the alcohols and unsaturatedhydrocarbon may be reduced to alkanes, thereby forming a more desirablehydrocarbon product having low levels of olefins, aromatics or alcohols.

The finishing step will generally be a hydrogenation reaction thatremoves the remaining carbonyl group or hydroxyl group. In such event,any one of the hydrogenation catalysts described above may be used. Suchcatalysts may include any one or more of the following metals, Cu, Ni,Fe, Co, Ru, Pd, Rh, Pt, Ir, Os, alloys or combinations thereof, alone orwith promoters such as Au, Ag, Cr, Zn, Mn, Sn, Cu, Bi, and alloysthereof, may be used in various loadings ranging from about 0.01 toabout 20 wt % on a support as described above.

In general, the finishing step is carried out at finishing temperaturesof between about 80° C. to 250° C., and finishing pressures in the rangeof about 100 psig to 2000 psig. The finishing step may be conducted inthe vapor phase or liquid phase, and may use in situ generated H₂,external H₂, recycled H₂, or combinations thereof, as necessary.

Other factors, such as the concentration of water or undesiredoxygenates, may also effect the composition and yields of the C₄₊compounds, as well as the activity and stability of the condensationcatalyst. In such event, the process may include a dewatering step thatremoves a portion of the water prior to condensation, or a separationunit for removal of the undesired oxygenates. For instance, a separatorunit, such as a phase separator, extractor, purifier or distillationcolumn, may be installed prior to the condensation step so as to removea portion of the water from the reactant stream containing theoxygenates. A separation unit may also be installed to remove specificoxygenates to allow for the production of a desired product streamcontaining hydrocarbons within a particular carbon range, or for use asend products or in other systems or processes.

C₄₊ Compounds

The practice of the present invention results in the production of C₄₊alkanes, C₄₊ alkenes, C₅₊ cycloalkanes, C₅₊ cycloalkenes, aryls, fusedaryls, C₄₊ alcohols, C₄₊ ketones, and mixtures thereof. The C₄₊ alkanesand C₄₊ alkenes have from 4 to 30 carbon atoms (C₄₋₃₀ alkanes and C₄₋₃₀alkenes) and may be branched or straight chained alkanes or alkenes. TheC₄₊ alkanes and C₄₊ alkenes may also include fractions of C₄₋₉, C₇₋₁₄,C₁₂₋₂₄ alkanes and alkenes, respectively, with the C₄₋₉ fractiondirected to gasoline, the C₇₋₁₄ fraction directed to jet fuels, and theC₁₂₋₂₄ fraction directed to diesel fuel and other industrialapplications. Examples of various C₄₊ alkanes and C₄₊ alkenes include,without limitation, butane, butane, pentane, pentene, 2-methylbutane,hexane, hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane,2,3-dimethylbutane, heptane, heptene, octane, octene,2,2,4,-trimethylpentane, 2,3-dimethyl hexane, 2,3,4-trimethylpentane,2,3-dimethylpentane, nonane, nonene, decane, decene, undecane, undecene,dodecane, dodecene, tridecane, tridecene, tetradecane, tetradecene,pentadecane, pentadecene, hexadecane, hexadecane, heptyldecane,heptyldecene, octyldecane, octyldecene, nonyldecane, nonyldecene,eicosane, eicosene, uneicosane, uneicosene, doeicosane, doeicosene,trieicosane, trieicosene, tetraeicosane, tetraeicosene, and isomersthereof.

The C₅₊ cycloalkanes and C₅₊ cycloalkenes have from 5 to 30 carbon atomsand may be unsubstituted, mono-substituted or multi-substituted. In thecase of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₁₊ alkylene, astraight chain C₂₊ alkylene, a phenyl or a combination thereof. In oneembodiment, at least one of the substituted groups include a branchedC₃₋₁₂ alkyl, a straight chain C₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, astraight chain C₁₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene, a phenylor a combination thereof. In yet another embodiment, at least one of thesubstituted groups include a branched C₃₋₄ alkyl, a straight chain C₁₋₄alkyl, a branched C₃₋₄ alkylene, straight chain C₁₋₄ alkylene, straightchain C₂₋₄ alkylene, a phenyl or a combination thereof. Examples ofdesirable C₅₊ cycloalkanes and C₅₊ cycloalkenes include, withoutlimitation, cyclopentane, cyclopentene, cyclohexane, cyclohexene,methyl-cyclopentane, methyl-cyclopentene, ethyl-cyclopentane,ethyl-cyclopentene, ethyl-cyclohexane, ethyl-cyclohexene, and isomersthereof.

Aryls will generally consist of an aromatic hydrocarbon in either anunsubstituted (phenyl), mono-substituted or multi-substituted form. Inthe case of mono-substituted and multi-substituted compounds, thesubstituted group may include a branched C₃₊ alkyl, a straight chain C₁₊alkyl, a branched C₃₊ alkylene, a straight chain C₂₊ alkylene, a phenylor a combination thereof. In one embodiment, at least one of thesubstituted groups include a branched C₃₋₁₂ alkyl, a straight chainC₁₋₁₂ alkyl, a branched C₃₋₁₂ alkylene, a straight chain C₂₋₁₂ alkylene,a phenyl or a combination thereof. In yet another embodiment, at leastone of the substituted groups include a branched C₃₋₄ alkyl, a straightchain C₁₋₄ alkyl, a branched C₃₋₄ alkylene, straight chain C₂₋₄alkylene, a phenyl or a combination thereof. Examples of various arylsinclude, without limitation, benzene, toluene, xylene (dimethylbenzene),ethyl benzene, para xylene, meta xylene, ortho xylene, C₉ aromatics.

Fused aryls will generally consist of bicyclic and polycyclic aromatichydrocarbons, in either an unsubstituted, mono-substituted ormulti-substituted form. In the case of mono-substituted andmulti-substituted compounds, the substituted group may include abranched C₃₊ alkyl, a straight chain C₁₊ alkyl, a branched C₃₊ alkylene,a straight chain C₂₊ alkylene, a phenyl or a combination thereof. Inanother embodiment, at least one of the substituted groups include abranched C₃₋₄ alkyl, a straight chain C₁₋₄ alkyl, a branched C₃₋₄alkylene, straight chain C₂₋₄ alkylene, a phenyl or a combinationthereof. Examples of various fused aryls include, without limitation,naphthalene, anthracene, tetrahydronaphthalene, anddecahydronaphthalene, indane, indene, and isomers thereof.

The C₄₊ alcohols may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ alcohols may be acompound according to the formula R¹—OH, wherein R¹ is a member selectedfrom the group consisting of a branched C₄₊ alkyl, straight chain C₄₊alkyl, a branched C₄₊ alkylene, a straight chain C₄₊ alkylene, asubstituted C₅₊ cycloalkane, an unsubstituted C₅₊ cycloalkane, asubstituted C₅₊ cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl,a phenyl and combinations thereof. Examples of desirable C₄₊ alcoholsinclude, without limitation, butanol, pentanol, hexanol, heptanol,octanol, nonanol, decanol, undecanol, dodecanol, tridecanol,tetradecanol, pentadecanol, hexadecanol, heptyldecanol, octyldecanol,nonyldecanol, eicosanol, uneicosanol, doeicosanol, trieicosanol,tetraeicosanol, and isomers thereof.

The C₄₊ ketones may also be cyclic, branched or straight chained, andhave from 4 to 30 carbon atoms. In general, the C₄₊ ketone may be acompound according to the formula

wherein R³ and R⁴ are independently a member selected from the groupconsisting of a branched C₃₊ alkyl, a straight chain C₁₊ alkyl, abranched C₃₊ alkylene, a straight chain C₂₊ alkylene, a substituted C₅₊cycloalkane, an unsubstituted C₅₊ cycloalkane, a substituted C₅₊cycloalkene, an unsubstituted C₅₊ cycloalkene, an aryl, a phenyl and acombination thereof. Examples of desirable C₄₊ ketones include, withoutlimitation, butanone, pentanone, hexanone, heptanone, octanone,nonanone, decanone, undecanone, dodecanone, tridecanone, tetradecanone,pentadecanone, hexadecanone, heptyldecanone, octyldecanone,nonyldecanone, eicosanone, uneicosanone, doeicosanone, trieicosanone,tetraeicosanone, and isomers thereof.

The lighter fractions of the above, primarily C₄-C₉, may be separatedfor gasoline use. Moderate fractions, such as C₇-C₁₄, may be separatedfor jet fuel, while heavier fractions, i.e., C₁₂-C₂₄, may be separatedfor diesel use. The heaviest fractions may be used as lubricants orcracked to produce additional gasoline and/or diesel fractions. The C₄₊compounds may also find use as industrial chemicals, whether as anintermediate or an end product. For example, the aryls toluene, xylene,ethyl benzene, para xylene, meta xylene, ortho xylene may find use achemical intermediates for the product of plastics and other products.Meanwhile, the C₉ aromatics and fused aryls, such as naphthalene,anthracene, tetrahydronaphthalene, and decahydronaphthalene, may finduse as solvents in industrial processes.

Catalyst Supports

In various embodiments above, the catalyst systems include a supportsuitable for suspending the catalyst in the feedstock solution. Thesupport should be one that provides a stable platform for the chosencatalyst and the reaction conditions. The support may take any formwhich is stable at the chosen reaction conditions to function at thedesired levels, and specifically stable in aqueous feedstock solutions.Such supports include, without limitation, carbon, silica,silica-alumina, alumina, zirconia, titania, ceria, vanadia, nitride,boron nitride, heteropolyacids, hydroxyapatite, zinc oxide, chromia, andmixtures thereof. Nanoporous supports such as zeolites, carbonnanotubes, or carbon fullerene may also be used.

One particularly preferred catalyst support is carbon, especially carbonsupports having relatively high surface areas (greater than 100 squaremeters per gram). Such carbons include activated carbon (granulated,powdered, or pelletized), activated carbon cloth, felts, or fibers,carbon nanotubes or nanohorns, carbon fullerene, high surface areacarbon honeycombs, carbon foams (reticulated carbon foams), and carbonblocks. The carbon may be produced via either chemical or steamactivation of peat, wood, lignite, coal, coconut shells, olive pits, andoil based carbon. Another preferred support is granulated activatedcarbon produced from coconuts. In one embodiment, the APR anddeoxygenation catalyst system consists of Pt on carbon, with the Ptbeing further alloyed or admixed with Ni, Ru, Cu, Fe, Rh, Re, alloys andcombinations thereof.

Another preferred catalyst support is zirconia. The zirconia may beproduced via precipitation of zirconium hydroxide from zirconium salts,through sol-gel processing, or any other method. The zirconia ispreferably present in a crystalline form achieved through calcination ofthe precursor material at temperatures exceeding 400° C. and may includeboth tetragonal and monoclinic crystalline phases. A modifying agent maybe added to improve the textural or catalytic properties of thezirconia. Such modifying agents include, without limitation, sulfate,tungstenate, phosphate, titania, silica, and oxides of Group IIIBmetals, especially Ce, La, or Y. In one embodiment, the APR anddeoxygenation catalyst consists of Pt on a primarily tetragonal phasesilica modified zirconia, with the Pt being further alloyed or admixedwith Ni, Ru, Cu, Fe, Rh, Re, alloys and combinations thereof.

Yet another preferred catalyst support is titania. The titania may beproduced via precipitation from titanium salts, through sol-gelprocessing, or any other method. The titania is preferably present in acrystalline form and may include both anatase and rutile crystallinephases. A modifying agent may be added to improve the textural orcatalytic properties of the titania. Such modifying agents include,without limitation, sulfate, silica, and oxides of Group IIIB metals,especially Ce, La, or Y. In one embodiment, the APR and oxygenateforming catalyst system consists of Ru on a primarily rutile phasetitania, with the Ru being further alloyed or admixed with Ge, Bi, B,Ni, Sn, Cu, Fe, Re, Rh, Pt, alloys and combinations thereof.

Another preferred catalyst support is silica. The silica may beoptionally combined with alumina to form a silica-alumina material. Inone embodiment, the APR catalyst system is Pt on silica-alumina orsilica, with the Pt being further alloyed or admixed with Ni, Ru, Cu,Fe, Rh, Re, alloys and combinations thereof. In another embodiment, theAPR catalyst system is Ni on silica-alumina or silica, with the nickelbeing further alloyed or admixed with Sn, Ge, Bi, Bu, Cu, Re, Ru, Fe,alloys and combinations thereof.

The support may also be treated or modified to enhance its properties.For example, the support may be treated, as by surface-modification, tomodify surface moieties, such as hydrogen and hydroxyl. Surface hydrogenand hydroxyl groups can cause local pH variations that affect catalyticefficiency. The support may also be modified, for example, by treatingit with sulfates, phosphates, tungstenates, silanes, lanthanides, alkalicompounds or alkali earth compounds. For carbon supports, the carbon maybe pretreated with steam, oxygen (from air), inorganic acids or hydrogenperoxide to provide more surface oxygen sites. The preferredpretreatment would be to use either oxygen or hydrogen peroxide. Thepretreated carbon may also be modified by the addition of oxides ofGroup IVB and Group VB. It is preferred to use oxides of Ti, V, Zr andmixtures thereof.

The catalyst systems, whether alone or mixed together, may be preparedusing conventional methods known to those in the art. Such methodsinclude incipient wetting, evaporative impregnation, chemical vapordeposition, wash-coating, magnetron sputtering techniques, and the like.The method chosen to fabricate the catalyst is not particularly criticalto the function of the invention, with the proviso that differentcatalysts will yield different results, depending upon considerationssuch as overall surface area, porosity, etc.

Supplemental Materials

Supplemental materials and compositions (“supplements”) may be added tothe feedstock solution at various stages of the process in order toenhance the reaction or to drive it to the production of the desiredreaction products. Supplements may include, without limitation, acids,salts and additional hydrogen or feedstock. Such supplements may beadded directly to the feedstock stream prior to or contiguous withcontacting the relevant catalyst, or directly to the reaction bed forthe appropriate reactions.

In one embodiment, the supplement may include an additional feedstocksolution for providing additional oxygenated hydrocarbons for oxygenateformation. The feedstock may include any one or more oxygenatedhydrocarbons listed above, including any one or more sugar alcohols,glucose, polyols, glycerol or saccharides. For instance, thesupplemental material may include glycerol. In this embodiment, crudeglycerol is used to initiate the reaction and to produce hydrogen so asto avoid polluting the deoxygenation catalyst with contaminants from thecrude glycerol. Purified glycerol is then added to the feedstocksolution prior to or at the same time the original feedstock solution isplaced in contact with the deoxygenation catalyst to increase theoxygenated hydrocarbons available for processing. It is anticipated thatthe opposite may be employed with the crude glycerol serving as thesupplement depending on the characteristics of the APR catalyst anddeoxygenation catalyst.

In another embodiment, the supplement may include additional oxygenatesfor the condensation reaction. The oxygenates may include any one ormore oxygenates listed above. For instance, the supplemental materialmay include a propyl alcohol. In this embodiment, the propyl alcohol maybe produced in a parallel system from a glycerol feedstock and thencombined with oxygenates produced by the processing of a sorbitolfeedstock in order to provide a reactant stream most effective toproduce a product containing a combination of C₆₋₁₂ hydrocarbons.

In yet another embodiment, the supplemental material may includerecycled oxygenates and/or oxygenated hydrocarbons not fully reactedduring the production process. The oxygenates and oxygenatedhydrocarbons may include any one or more of oxygenates and oxygenatedhydrocarbons listed above.

In still yet another embodiment, the supplemental material may includeacids and salts added to the process. The addition of acidic compoundsmay provide increased selectivity to the desired oxygenates and,ultimately, C₄₊ compounds. Water-soluble acids may include, withoutlimitation, nitrate, phosphate, sulfate, chloride salts, and mixturesthereof. If an optional acidic modifier is used, it is preferred that itbe present in an amount sufficient to lower the pH of the aqueous feedstream to a value between about pH 1.0 and about pH 4.0. Lowering the pHof a feed stream during oxygenate formation in this manner may increasethe proportion of diols, polyols, ketones or alcohols for furthercondensation.

Reactor System

The reactions described herein may be carried out in any reactor ofsuitable design, including continuous-flow, batch, semi-batch ormulti-system reactors, without limitation as to design, size, geometry,flow rates, etc. The reactor system may also use a fluidized catalyticbed system, a swing bed system, fixed bed system, a moving bed system,or a combination of the above. Preferably, the present invention ispracticed utilizing a continuous-flow system at steady-stateequilibrium.

In a continuous flow system, the reactor system includes at least areforming bed adapted to receive an aqueous feedstock solution toproduce hydrogen, a deoxygenation bed adapted to produce oxygenates fromthe hydrogen and a portion of the feedstock solution, and a condensationbed to produce C₄₊ compounds from the oxygenates. The reforming bed isconfigured to contact the aqueous feedstock solution in a vapor phase orliquid phase with the APR catalyst to provide hydrogen in a reactantstream. The deoxygenation bed is configured to receive the reactantstream for contact with the deoxygenation catalyst and production of thedesired oxygenates. The condensation bed is configured to receive thereactant stream for contact with the condensation catalyst andproduction of the desired C₄₊ compounds. For systems not involving anAPR hydrogen production step, the reforming bed may be removed. Forsystems not involving a hydrogen or oxygenate production step, thereforming and deoxygenation beds may be removed. Because the APRcatalyst, deoxygenation catalyst and condensation catalyst may also beatomically identical, the catalysts may exist as the same bed. Forsystems with a hydrogenation or hydrogenolysis step, an additionalreaction bed may be included prior to the deoxygenation and/or reformingbed. For systems with a finishing step, an additional reaction bed forconducting the finishing process may be included after the condensationbed.

In systems producing both hydrogen and oxygenates, the condensation bedmay be positioned within the same reactor vessel along with thereforming bed or in a second reactor vessel in communication with afirst reactor vessel having the reforming bed. The condensation bed maybe within the same reactor vessel along with the reforming ordeoxygenation bed or in a separate reactor vessel in communication withthe reactor vessel having the deoxygenation bed. Each reactor vesselpreferably includes an outlet adapted to remove the product stream fromthe reactor vessel. In systems including a hydrogenation step orhydrogenolysis step, the hydrogenation or hydrogenolysis reaction bedmay be within the same reactor vessel along with the reforming ordeoxygenation bed or in a separate reactor vessel in communication withthe reactor vessel having the reforming bed and/or deoxygenation bed.For systems with a finishing step, the finishing reaction bed may bewithin the same reactor vessel along with the condensation bed or in aseparate reactor vessel in communication with the reactor vessel havingthe condensation bed.

The reactor system may also include additional outlets to allow for theremoval of portions of the reactant stream to further advance or directthe reaction to the desired reaction products, and to allow for thecollection and recycling of reaction byproducts for use in otherportions of the system. The reactor system may also include additionalinlets to allow for the introduction of supplemental materials tofurther advance or direct the reaction to the desired reaction products,and to allow for the recycling of reaction byproducts for use in thereforming process. For example, the system may be designed such thatexcess hydrogen is produced over the APR catalyst, with a portion of theexcess hydrogen removed and reintroduced downstream in the process tosupplement the reaction of the oxygenates over the condensation catalystor the finishing of the condensation product to arrive at the desiredC₄₊ compounds. Alternatively, the system may be designed such thatexcess hydrogen is produced over the APR catalyst, with a portion of theexcess hydrogen removed and used in other upstream processes, such asfeedstock pretreatment processes and hydrogenation or hydrogenolysisreactions.

The reactor system may also include elements which allow for theseparation of the reactant stream into different components which mayfind use in different reaction schemes or to simply promote the desiredreactions. For instance, a separator unit, such as a phase separator,extractor, purifier or distillation column, may be installed prior tothe condensation step to remove water from the reactant stream forpurposes of advancing the condensation reaction to favor the productionof hydrocarbons. A separation unit may also be installed to removespecific oxygenates to allow for the production of a desired productstream containing hydrocarbons within a particular carbon range, or foruse as end products or in other systems or processes.

In one embodiment, the reaction system is configured such that the flowdirection of the aqueous feedstock solution is established to ensuremaximal interaction with the in-situ generated H₂. The reactor may bedesigned so that the reactant stream flows horizontally, vertical ordiagonally to the gravitational plane so as to maximize the efficiencyof the system. In systems where the reactant stream flows vertically ordiagonally to the gravitational plan, the stream may flow either againstgravity (up-flow system), with gravity (down-flow system), or acombination of both. In one preferred embodiment, the APR and/ordeoxygenation reactor vessel is designed as an up-flow system while thecondensation reactor vessel is designed as a down-flow system. In thisembodiment, the feedstock solution first contacts a reforming bedcontaining the APR catalyst to produce in-situ generated H₂. Due to theconfiguration of the reactor, the APR H₂ is then able to, under certainconditions, percolate through a second reaction bed containing thedeoxygenation catalyst at a rate greater than or equal to the feedstocksolution to maximize the interaction of the feedstock solution with theH₂ and deoxygenation catalyst. The resulting reactant stream is thenfeed into the condensation reactor in a down-flow configuration forprocessing.

If the APR catalyst and deoxygenation catalyst are within a singlechamber, the APR catalyst and deoxygenation catalyst may be placed in astacked configuration to allow the feedstock solution to first contactthe APR catalyst and then the deoxygenation catalyst, or a series ofdeoxygenation catalysts depending on the desired reaction products. Thereaction beds for the APR catalyst and deoxygenation catalyst, orcatalysts, may also be placed side-by-side dependent upon the particularflow mechanism employed. In either case, the feedstock solution may beintroduced into the reaction vessel through one or more inlets, and thendirected across the catalysts for processing. In another embodiment, thefeedstock solution is directed across the APR catalyst to produce APRH₂, and then both the APR H₂ and the remaining feedstock solution aredirected across the deoxygenation catalyst, or catalysts, to produce thedesired oxygenates. In a parallel configuration, the feedstock solutionmay be separated to direct a first portion of the feedstock solution tothe reforming bed where APR H₂ is produced, and a second portion to adeoxygenation bed where the desired oxygenates are produced using the insitu generated APR H₂. Alternatively, the reactor may be configured toaccommodate the use of two separate feedstock solutions, with the firstfeedstock solution directed to the APR reactor vessel and the secondfeedstock solution directed to the deoxygenation reactor vessel. In asequential configuration, the reactor may be designed so that thefeedstock solution flows through the APR reactor vessel and into thedeoxygenation reactor vessel. In embodiments employing a combinedAPR/deoxygenation catalyst, the generation of APR H₂ and oxygenatesoccurs simultaneously. In either of these systems, because the APR H₂ isproduced in-situ, the pressure is provided by a pumping mechanism thatalso drives the feedstock solution through the reactor chambers.

FIG. 6 is a process diagram illustrating one potential reactor systemuseful in practicing the invention. A feed stream of oxygenatedhydrocarbons 1 (with or without water) is mixed with a stream ofrecycled water and recycled oxygenates at 2 to provide an aqueousfeedstock solution 3. The feedstock solution 3 is then hydrogenated in apretreatment step 4 to provide a feedstock solution 5 that is morereadily converted to the desired oxygenates. The H₂ for thehydrogenation step may derive from an external source 22 or hydrogenrecycled from the system as illustrated in steps 13-21 below. Thefeedstock solution 5 is reacted in a reactor vessel 8 that contains anAPR catalyst and a deoxygenation catalyst to produce product stream 7containing water, H₂, carbon dioxide, hydrocarbons and oxygenates. Waterin product stream 7 is then removed at 8 to provide a product stream 10containing oxygenates, hydrogen, carbon dioxide and hydrocarbons. Waterfrom dewatering step 8 is then recycled at 9 and 15 for mixing with thestream of oxygenated hydrocarbons at 2. Product stream 10 is then passedthrough reactor vessel 11, which includes a condensation catalyst toproduce product stream 12 containing C₄₊ compounds, water, H₂ and carbondioxide. Product stream 12 is then passed through a three-phaseseparator 13 to separate the non-condensable gases 16 (i.e., hydrogen,carbon dioxide, methane, ethane, and propane) from the hydrocarbonproduct stream 14 containing C₄₊ compounds and water 15. Water 15 fromthe separator can be either recycled or exported from the system. Thenon-condensable gas stream 16 can be passed through a separation unit 17to provide a purified H₂ stream 19 and a raffinate stream 18 containingcarbon dioxide, methane, ethane, propane, and some hydrogen. Thepurified H₂ 19 may then be either exported from the system at 20 orpassed through a recycle compressor 21 to provide recycled hydrogenstream 23.

In another preferred reactor system, illustrated in FIG. 7, a firstreactor system is provided for converting the desired feedstock solutionto C₄₊ compounds. The feedstock solution is stored in tank 1 and thenpassed through feed line 2 into charge pump 3. Charge pump 3 increasesthe pressure of the feedstock solution to the desired reaction pressure,e.g., 600 psi, and then discharges the solution through line 4 into anelectric preheater 5 that heats the feed to the desired inlettemperature. The heated solution 6 is then passed into the process sideof a reactor having essentially a tube-within-tube configuration (tube 7within tube 8). Depending on the pressure of the reactor and thetemperatures at which the several stages are operated, the reactantstream flowing through the reactor tube 7 will generally be maintainedsubstantially in the liquid phase throughout, but may vaporize due tothe heat of the condensation of the distal portion 7 b such that most ofthe product exiting the outlet end of the reactor through line 15 is invapor form.

The stages and stage regions of the reactor tube 7 include anAPR/deoxygenation catalyst (combined) and a condensation catalyst, eachpacked in successive catalytic beds (i.e., one on top of another). Inthis example, reactor tube 7 contains an APR/deoxygenation catalyst inthe proximal portion 7 a of reactor tube 7 and a condensation catalystat the distal portion 7 b. The catalyst system is supported at thebottom with small mesh stainless steel spheres setting on a stainlesssteel frit. Stainless steel spheres are also place on top of thecatalyst bed. To facilitate separation of spent catalyst for recyclingor regeneration, the catalyst beds are separated by means of a porousmaterial, such as glass wool. The reactor may also be physicallyseparated in separate tubes with conduits connecting the tubes to permitcontinuous flow. Such an arrangement may permit better thermalmanagement, allowing optimization of temperature according to therequirements of the reactions in the several reactor stages.

The APR reaction is typically endothermic, while the condensationreaction is typically highly exothermic. Preferably, the reactor systempermits the heat generated in the condensation reaction to be used toheat the APR and deoxygenation reactions. An advantage of conductingboth of these reactions together is that heat is immediately transferredfrom the exothermic condensation reaction to the endothermicreforming/deoxygenation reactions.

The process tube 7 is preferably formed from a heat-conducting materialconfigured to transfer heat from the distal portion 7 b to the proximalportion 7 a. In addition, the process tube may be heated with hot oil orhot air flowing through an annular space between process tube 7 andouter tube 8. The hot air may be generated by heating ambient air from ablower 10 with an electrical heater 12 and sent to the reactor throughline 13. Hot oil may also be used and generated by a heater and pump(not shown) and sent to the reactor through line 13 as well. The flowconfiguration for this system is such that the hot air (or oil) in tube8 flows countercurrent to the process fluid in tube 7. Accordingly, thereactor tube 7 is preferably warmer at the bottom than at the top.

Alternatively, the process tube 7 may be separated into two separatetubes or regions to facilitate the optimization of reaction conditionsseparately for the APR and deoxygenation reactions, and for thecondensation reaction. For example, the separation of spent catalyst forregeneration may be simplified in this manner. In a two-region secondstage in a vertical reactor, heat generated by condensation in the lowerregion may be permitted to move by convection to the upper region foruse in the reformation reaction. The second region may also beconfigured to provide a continuous or step-wise gradient of mixedreformation and condensation catalysts, with more reformation catalystat the upper end and more condensation catalyst at the lower end.

The effluent 15 from reactor tube 7 includes gaseous products (such ashydrogen, CO and CO₂) as well as aqueous and organic liquid products.The effluent is cooled to ambient temperature using a water cooled tubein a tube condenser 16. Effluent 17 from the condenser 16 is thendirected to a three-phase separator to separate the product phases: thenon-condensable gas 18 (upper phase), a lower density organic-liquidphase 19 (middle phase) and a higher-density aqueous-liquid phase 20(lower phase). The system pressure is maintained by controlling the flowof non-condensable gas through line 21. The liquid level is maintainedby controlling the flow of the aqueous-phase components through line 23.The organic-liquid phase is then skimmed off the top of the aqueousphase through line 22.

The aqueous phase 20 is withdrawn through line 23. If the aqueous phase20 contains significant levels of residual oxygenates (i.e., products ofincomplete reformation), the aqueous phase 20 may be conducted throughline 23 back to feed source 6 where it is used for feedstock directedback into the reactor. In this way, the carbon content and energy valueof the intermediate processes are recovered.

The middle phase 19 contains C₅₊ compounds. Typically, this phasecontains hydrocarbons and mono-oxygenates ranging primarily from C₄ toC₃₀. Lighter fractions, primarily C₄-C₉, may be separated for gasolineuse. The moderate fraction, i.e., C₁₂-C₂₄, may be separated for use asjet fuel. Heavier fractions, i.e., C₁₂-C₂₄, may be separated for dieseluse. The heaviest fractions may be used as lubricants or cracked toproduce additional gasoline and/or diesel fractions. Each of the abovemay also be used for industrial chemical applications.

The vapor phase 18 contains hydrogen and other APR reaction products,such as carbon monoxide, carbon dioxide, methane, ethane, propane,butane, pentane, and/or hexane gas. Part of this gas is purged from thesystem to prevent the build-up of light hydrocarbons and CO₂ in thesystem through line 22. The gases may also be used as a fuel source forpurposes of providing heat to the reactor system. In terms of scaled-upproduction, after start-up, the reactor systems could be processcontrolled, and the reactions would proceed at steady-state equilibrium.

The following examples are included solely to provide a more completedisclosure of the subject invention. Thus, the following examples serveto illuminate the nature of the invention, but do not limit the scope ofthe invention disclosed and claimed herein in any fashion.

EXAMPLES Exemplary Reactor Systems Example 1

FIG. 8 shows a process diagram illustrating one reactor system useful inpracticing the present invention. A feedstock tank 1 acts as a reservoirfor holding the feedstock solutions. The feedstock solution is deliveredfrom the feedstock tank 1 to feed pump 3 through feed line 2, where itis then passed through discharge line 4 to preheater 5. The preheater 5may be a heat exchanger heated by an electrical resistance heater, orany other heat exchanger known in the art. The preheated feed is thenpassed through line 6 and, in some cases, combined with hydrogen 7before entering reactor 9 through line 8. One illustration of apotential reactor 9 is set forth in FIG. 11 and more fully described inExample 4 below.

The temperature of the walls of reactor 9 is maintained by blockheaters, 10 a, 10 b, 10 c, and 10 d, in this case, electrical resistanceheaters. Upon exiting the reactor 9, reaction products enter the reactoroutlet line 11 and are cooled to near ambient temperature in reactorproduct cooler 12, resulting in a potential three phase product stream.From reactor product cooler 12, the reaction products proceed throughline 13 to pressure regulating valve 14, which is used to control thepressure at the reactor outlet if required.

After valve 14, the products enter a phase separator 16 through line 15where it segregates into three separate phases: (1) non-condensable gascomponents 17 containing predominately hydrogen, carbon dioxide,methane, ethane, and propane; (2) an organic liquid fraction 18containing both hydrocarbons and C₃₋₃₀ alcohols, ketones and carboxylicacids; and (3) an aqueous layer 19 containing mostly water and watersoluble oxygenated compounds, such as ethanol, isopropanol, acetone,propanol and acetic acid. The non-condensable gas fraction 17 may berouted through the gas product line 20 to pressure reducing valve 21.The pressure of separator 16 is maintained by pressure reducing valve21. In an alternate mode of operation, the separator 16 may bemaintained at a pressure nearly the same as the reactor outlet byopening or eliminating valve 14. In the alternate mode of operation, thereactor outlet pressure is then controlled by action of pressurereducing valve 21. Gas flow rate and composition are measured uponexiting the system through line 22.

The organic liquid fraction 18 exits the separator through line 23before entering organic draw-off valve 24. The level of organic phasewithin the separator is controlled by adjustment of valve 24. The flowrate and composition of the organic fraction are determined after theorganic fraction exit the system through line 25. The aqueous liquidfraction 19 exits the separator through line 26 before enteringseparator bottoms draw-off valve 27. The level of aqueous phase withinthe separator is controlled by adjustment of valve 27.

The flow rate and composition of the aqueous fraction may be determinedafter the aqueous fraction exits the system through line 28. In analternate mode of operation, both the organic liquid fraction 18 and theaqueous liquid fraction 19 exit the system through the bottom draw-offvalve 27 of the separator and line 28 before being separated in adecanter for measurement of the individual phase compositions and flowrates.

In all cases, the alternate modes of operation do not affect thecatalytic processes being investigated. The alternate modes of operationmay be employed as deemed prudent to achieve optimal control of theprocess, depending on the relative flow rates of the gaseous phase 17,organic liquid phase 18, and aqueous phase 19.

Prior to initiating a flow of feed to the reactors, unless otherwisenoted, catalysts were reduced in a stream of flowing hydrogen at 400°C., regardless of whether a reduction was completed prior to loading thecatalyst into the reactors.

Example 2

FIG. 9 shows a process diagram illustrating another reactor systemuseful for practicing the present invention. This reactor configurationcontains two separate reactors with the capability of operating bothreactors in series or operating only the first reactor. In addition,this configuration allows the catalyst in the second reactor to be takenoff line and regenerated in situ. After regeneration, the second reactormay be returned to service without impacting the first reactoroperation.

The reactor is similar to the reactor of Example 1, except that thereaction products from reactor product cooler 12 could be routed intothe second reactor through line 14 or routed to bypass the secondreactor by passing into line 44. When utilizing the second reactor, flowwould proceed from line 14 to pressure regulating valve 15. Pressureregulating valve 15 may be used to control the pressure at the outlet ofthe first reactor. From pressure regulating valve 15 the flow proceedsto the second reactor inlet isolation valve 17 and into line 18. Fromline 18 the flow continues to line 19 and into the second reactorpreheater 20. In the illustrated embodiment, preheater 20 is a heatexchanger heated by an electrical resistance heater.

The preheated feed is then passed through line 19 into the secondreactor 22, which is more fully described in Example 4. The temperatureof the wall of reactor 22 is maintained by block heaters, 23 a, 23 b, 23c, and 23 d, in this case, electrical resistance heaters. Upon exitingthe reactor, the reaction products enter the second reactor outlet line24 and are then cooled in second reactor product cooler 25. From secondreactor product cooler 26 the process flow may be routed through lines26 and 27 to second reactor outlet isolation valve 28, into lines 29followed by 30 and then into the product separator 31.

When operation of the second reactor is desired, valve 17 and valve 28are open while the second reactor bypass valve 45 is closed to preventthe flow from bypassing the second reactor. When operation of only thefirst reactor is desired, or when the second reactor is beingregenerated, valve 17 and valve 28 are closed while valve 45 is open.When the second reactor is bypassed, the first reactor product flowsdirectly from line 13 into line 44, through bypass valve 45, into line46 and on to line 30. In either case, whether the second reactor is inoperation or bypassed, the flow would proceed from line 30 into theproduct separator.

In phase separator 31, reaction products are separated into a gaseousfraction 32, an organic fraction 33, and an aqueous fraction 34 asdescribed above in Example 1. The gaseous fraction 32 is routed throughthe gas product line 35 to pressure reducing valve 36. The pressure ofseparator 31 is maintained by pressure reducing valve 36. When thesecond reactor 22 is in service, the pressure at the second reactor 22outlet is controlled by action of pressure reducing valve 36. When thesecond reactor 22 is bypassed, the pressure at the outlet of the firstreactor 9 is controlled by action of pressure reducing valve 36.

Gas flow rate and composition are measured upon exiting the systemthrough line 37. The organic liquid fraction 33 exits the separatorthrough line 38 before entering organic draw-off valve 39. The level oforganic phase within the separator is controlled by adjustment of valve39. The flow rate and composition of the organic fraction are determinedafter the organic fraction exits the system through line 40. The aqueousliquid fraction 34 exits the separator through line 41 before enteringseparator bottoms draw-off valve 42. The level of aqueous phase withinthe separator is controlled by adjustment of valve 42. The flow rate andcomposition of the aqueous fraction are determined after the aqueousfraction exits the system through line 43. In an alternate mode ofoperation, both the organic liquid fraction 33 and the aqueous liquidfraction 34 exit the system through the separator bottoms draw-off valve42 and line 43 before being separated in a decanter for measurement ofthe individual phase compositions and flow rates. In all cases, thealternate modes of operation do not affect the catalytic processes beinginvestigated. The alternate modes of operation are employed as deemedprudent to achieve optimal control of the process, depending on therelative flow rates of the gaseous phase 35, organic liquid phase 33,and aqueous phase 34.

Example 3

FIG. 10 shows a process diagram illustrating a dual feed pump reactorsystem useful for practicing the present invention. A dual feed pumpsystem is used when the desired mix of feed components would not existin a single liquid phase. For example, when a mix of 50% by weight2-pentanol and 50% by weight water is the desired feed, two feed pumpsare used, one to deliver 2-pentanol and the other to deliver water. Asimilar system may also be used to mix feedstock derived from twoseparate sources, such as a virgin feedstock and an oxygenatedhydrocarbon feedstock derived from an effluent stream of the reactorsystem itself.

First feedstock tank 1 acts as a reservoir for a first feedstocksolution, while second feedstock tank 40 acts as a reservoir for asecond feedstock solution. A first feed is delivered from firstfeedstock tank 1 to first feed pump 3 through first feed line 2. Thefirst feed is then passed through the first feed pump discharge line 4to combined feed line 44. The second feed is delivered from the secondfeedstock tank 40 to second feed pump 42 through second feed line 41.The second feed is then passed through second feed pump discharge line43 to combined feed line 44. From combined feed line 44 the combinedfeed passes into preheater 5. All other elements are as set forth inExample 1, except that the aqueous phase 19 may be recycled to feedstocktank 40 for further processing or used in other processes.

Example 4

FIG. 11 shows a schematic illustration of one type of reactor which maybe employed in reactor systems as described in Examples 1, 2 and 3.Reactor tube 1 is composed of 316 stainless steel with either an insidediameter of 8.5 mm or an inside diameter of 21.2 mm, depending on theexperiment. Inlet line 2 is provided to allow feedstock or intermediateproduct, such as oxygenates, to enter the reactor. Outlet line 3 isprovided to remove product from the reactor. Inlet frit 4, composed ofstainless steel, acts to secure the beds of preheat media and catalystin place. Preheat media 5, consisting of stainless steel beads, acts asa zone to allow transfer of heat from the reactor walls so that the feedis at the desired temperature upon entering the catalyst 7. A stainlesssteel screen may be placed between preheat media 5 and catalyst 7 toprevent the materials from mixing. Catalyst 7 may be supported inposition by a second stainless steel frit 8.

A thermowell 9 may be installed in some cases to allow measurement ofthe temperatures within catalyst 7 and preheating zone 5. Control oftemperature at the reactor inlet is accomplished by the use of anexternal preheater prior to the feed entering the reactor through line2, and may be further adjusted by control of the heat transfer thatoccurs in the preheat media. In some cases, the preheat media is notrequired to achieve the desired temperature profile. Control of thereactor wall temperature is achieved by the use of external heaters incontact with the outer wall of the reactor. Independently controlledheating zones may be used to control the temperature of the reactor wallas desired.

Example 5 Analysis Techniques

Product streams from the examples described below were analyzed asfollows. The organic liquid phase was collected and analyzed usingeither gas chromatograph with mass spectrometry detection or flameionization detection. Component separation was achieved using a columnwith a bonded 100% dimethyl polysiloxane stationary phase. Relativeconcentrations of individual components were estimated via peakintegration and dividing by the sum of the peak areas for an entirechromatogram. Compounds were identified by comparison to standardretention times and/or comparison of mass spectra to a compiled massspectral database. Gas phase compositions were determined by gaschromatography with a thermal conductivity detector and flame ionizationor mass spectrometry detectors for other gas phase components. Theaqueous fraction was analyzed by gas chromatography with and without aderivatization of the organic components of the fraction using a flameionization detector. Product yields are represented by the feed carbonpresent in each product fraction. The weight hourly space velocity(WHSV) was defined as the weight of feed introduced into the system perweight of catalyst per hour, and based on the weight of the oxygenatedhydrocarbon feed only, excluding water present in the feed.

Production of Oxygenates Example 6 Hydrogenation Catalyst

A hydrogenation catalyst was prepared by adding an aqueous solution ofdissolved ruthenium nitrosyl nitrate to a carbon catalyst support (UUCarbon, Calgon, with particle sizes restricted to those that weremaintained on a 120 mesh screen after passing through an 60 mesh screen)to a target loading of 2.5% ruthenium. Water was added in excess of thepore volume and evaporated off under vacuum until the catalyst was freeflowing. The catalyst was then dried overnight at 100° C. in a vacuumoven.

Example 7 APR/Deoxygenation Catalyst

A combined APR and deoxygenation catalyst was prepared by dissolvinghexachloroplatinic acid and perrhenic acid in water and then adding themixture to a monoclinic zirconia catalyst support (NorPro Saint-Gobain,Product code SZ31164, with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen)using an incipient wetness technique to target a platinum loading of1.8% and a rhenium loading of 6.3% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight in a vacuum oven and subsequently calcined in a stream offlowing air at 400° C.

Example 8 Conversion of Sucrose to Oxygenates

The catalyst systems referenced in Examples 6 and 7 were investigatedfor the conversion of sucrose to an intermediate product containingoxygenates using the reactor system described in Example 1. The studywas conducted using a 21.2 mm internal diameter stainless steel tubereactor shown in Example 4, with an analysis completed as described inExample 5.

31 grams of hydrogenation catalyst from Example 6 and 76 grams of APRcatalyst from Example 7 were loaded into the reactor, with thehydrogenation catalyst on top of the APR catalyst, separated by astainless steel screen. External hydrogen was combined with the feedprior to the feed entering the reactor. Heaters external to the reactor,shown in FIG. 8 as 10 a, 10 b, 10 c, 10 d, were maintained at thefollowing reactor wall temperatures; 10 a-125° C., 10 b-200° C., 10c-265° C., 10 d-265° C., resulting in reactor bed temperatures ofapproximately ˜110-150° C. for hydrogenation, and 150-265° C. for theAPR/Deoxygenation catalyst. The ranges indicate the approximate reactorwall temperatures at the inlet and outlet of each catalyst bed,respectively. Results from the experiment across 39 hours of operationare shown in Table 1. The WHSV is based on the weight of theAPR/Deoxygenation catalyst. Total mono-oxygenates includes alcohols,ketones, tetrahydrofurans and cyclic mono-oxygenates. Cyclicmono-oxygenates includes compounds in which the ring does not includeoxygen, such as cyclopentanone and cyclohexanone. The fraction of feedcarbon contained within unknown components in the aqueous phase wasdetermined as the difference of carbon accounted for by known, measuredcomponents and the total organic carbon.

TABLE 1 Conversion of Sucrose to Oxygenates Across a Hydrogenation andAPR catalyst Hours on Stream 5 16 27 39 WHSV wt_(feed)/(wt_(catalyst)hr) 1.8 1.8 1.7 1.5 Added Hydrogen mol_(H2)/mol_(feed) 3.4 3.4 3.6 4.0Organic Phase Yield % of feed carbon 27 25 20 22 Breakdown of ReactorOutlet Composition Carbon Dioxide % of feed carbon 19.4 21.2 18.1 17.7Paraffins % of feed carbon 14.1 13.5 9.2 10.8 Mono-oxygenates % of feedcarbon 31.5 30.6 27.5 30.8 Alcohols % of feed carbon 11.1 11.8 11.2 11.6Ketones % of feed carbon 8.2 7.0 7.1 9.0 Tetrahydrofurans % of feedcarbon 10.6 10.7 8.1 8.6 Cyclic Mono-oxygenates % of feed carbon 1.6 1.11.1 1.5 Unknown Aqueous % of feed carbon 21.2 27.8 28.3 32.0 Species

Example 9 APR/Deoxygenation Catalyst

A catalyst was prepared as described in Example 7, except that thecatalyst support was a tetragonal zirconia (NorPro Saint-Gobain, Productcode SZ61152) with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen.

Example 10 APR/Deoxygenation Catalyst

Hexachloroplatinic acid and perrhenic acid dissolved in water were addedto a monoclinic zirconia catalyst support (NorPro Saint-Gobain, Productcode SZ61164, with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen)using an incipient wetness technique to target a platinum loading of1.9% and a rhenium loading of 1.8% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight in a vacuum oven and subsequently calcined in a stream offlowing air at 400° C.

Example 11 APR/Deoxygenation Catalyst

A catalyst was prepared as described in Example 7 except that thesupport was a hydrogen peroxide functionalized activated carbon. Thesupport was first prepared by adding activated carbon (Calgon UU 60×120mesh carbon) slowly to a 30% hydrogen peroxide solution, with themixture then left overnight. The aqueous phase was decanted and thecarbon was washed three times with deionized water, and then dried undervacuum at 100° C. A solution of hexachloroplatinic acid and perrhenicacid in water was then added to the support using an incipient wetnesstechnique to target a platinum loading of 1.8% and a rhenium loading of6.3% after subsequent decomposition of the metal precursors. Thepreparation was dried overnight in a vacuum oven at 100° C.

Example 12 Conversion of Sorbitol and Glycerol

The catalyst systems referenced in Example 9, Example 10, and Example11, were investigated for the conversion of sorbitol or glycerol to anintermediate product containing oxygenates using the reactorconfiguration described in Example 1, with an analysis completed asdescribed in Example 5. The study was conducted using the 8.5 mminternal diameter stainless steel tube reactor shown in Example 4. Inall cases, the reactor pressure was maintained at 625 psig. Reactorinlet and outlet temperatures, shown in Table 2 were controlled usingheaters external to the reactor as shown in FIG. 8 as 10 a, 10 b, 10 c,10 d. Results of these experiments are shown in Table 2.

Table 2 shows the impact of catalyst composition, feedstock composition,and operating conditions on the conversion performance. FIG. 12 showsthe carbon number distribution of the mono-oxygenates produced inExperiment D and Experiment E. The primary difference between these twoexperiments was the reaction temperature. For Experiment D,mono-oxygenates containing three or fewer carbon atoms predominatedwhile for Experiment E, a significant fraction of the mono-oxygenatescontained four or more carbon atoms, indicating that condensationreactions were occurring within the same reaction zone as the hydrogengeneration and deoxygenation reactions. The WHSV is based on the weightof the APR/Deoxygenation catalyst. The net hydrogen produced is thehydrogen present at the reactor outlet as H₂, which does not includehydrogen produced and consumed in situ. Total mono-oxygenates includealcohols, ketones, tetrahydrofurans and cyclic mono-oxygenates. Cyclicmono-oxygenates include compounds in which the ring does not includeoxygen, such as cyclopentanone and cyclohexanone. The fraction of feedcarbon contained within unknown components in the aqueous phase wasdetermined as the difference of carbon accounted for by known, measuredcomponents and the total organic carbon.

TABLE 2 Conversion of Polyols to Oxygenates Across a APR/DeoxygenationCatalyst Experiment A B C D E Feed 50% Sorbitol 50% Sorbitol 65%Sorbitol 50% Glycerol 50% Glycerol Catalyst Composition Example No. 11 910 10 10 WHSV wt_(feed)/ 2.1 1.8 1.7 1.5 1.5 (wt_(catalyst) hr) CatalystInlet Temp. ° C. 241 240 240 260 310 Catalyst Outlet ° C. 240 241 321260 350 Temperature Net Hydrogen mol_(H2)/mol_(feed) 0.6 0.9 0.7 1.2 0.7Produced Organic Phase Yield % of feed 17 24 38 0 38 carbon Breakdown ofReactor Outlet Composition Carbon Dioxide % of feed 32.4 34.0 23.5 31.316.0 carbon Paraffins % of feed 37.4 25.3 7.8 6.6 7.4 carbon TotalMono-oxygenates % of feed 33.9 32.9 40.0 45.9 41.0 carbon Alcohols % offeed 6.3 8.5 2.6 40.6 4.6 carbon Ketones % of feed 23.5 16.9 15.2 5.224.1 carbon Tetrahydrofurans % of feed 4.1 7.2 10.7 0.1 2.7 carbonCyclic % of feed 0.0 0.4 11.6 0.0 9.7 Monooxygenates carbon UnknownAqueous % of feed 1.2 7.8 15.8 30.4 10.7 Species carbon

Condensation of Oxygenates Using Basic Catalysts Example 13

A zinc aluminate catalyst support was prepared by mixing zinc oxidepowder and alumina powder (Dispal 18N4-80, Sasol North America, Houston,Tex.) to a target ratio of 1.0 moles of ZnO to 1 mole of Al₂O₃. Dilutenitric acid was then added at a level of 1 wt % HNO₃ to alumina. Thedough consistency of the mixture was adjusted with water addition toform a workable dough, which was then extruded using a laboratory scaleextruder. The extrudates were dried overnight under vacuum at 100° C.,then further dried at 200° C. for one hour under flowing air, and thensubsequently calcined at 750° C. for 4 hours under flowing air. Theresulting material was then ground and sieved. Material that wasmaintained on a 60 mesh screen after passing through an 18 mesh screenwas recovered.

Example 14

Hexachloroplatinic acid was added to the calcined material of Example 13using an incipient wetness impregnation technique to achieve a targetplatinum loading of 1.0 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 15

Palladium nitrate was added to the calcined material of Example 13 usingan incipient wetness impregnation technique to achieve a targetpalladium loading of 0.5 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 16

A copper zinc aluminate catalyst was prepared by mixing zinc oxide,copper (I) oxide, and alumina powder (Dispal 18N4-80) at a target ratioof 0.11 moles of CuO and 0.9 moles of ZnO to one mole of Al₂O₃. Dilutenitric acid was then added at a level of 1 wt % HNO₃ to alumina. Thedough consistency of the mixture was adjusted with water addition toform a workable dough, which was then extruded using a laboratory scaleextruder. The extrudates were dried overnight under vacuum at 100° C.,then further dried at 200° C. for one hour under flowing air, and thensubsequently calcined at 750° C. for 4 hours under flowing air. Theresulting material was then ground and sieved. Material that wasmaintained on a 60 mesh screen after passing through an 18 mesh screenwas recovered.

Example 17

A cesium modified silica-alumina catalyst was prepared by adding cesiumcarbonate dissolved in water to Siralox silica-alumina catalyst support(Sasol North America, Houston, Tex.). The target loading of cesium was25 wt % based on final catalyst weight. This material was dried for 24hours under vacuum at 100° C. and calcined at 500° C. for 6 hours underflowing air. After calcining, platinum was added using an incipientwetness impregnation technique to achieve a final platinum loading of 1wt %. After impregnation, the catalyst was dried and then calcined at500° C. for 6 hours under flowing air.

Example 18

A cerium modified silica was prepared by adding cerium nitrate solutionto a silica gel (Davisil grade 636, WR Grace Company) to a final loadingof 25 wt % CeO₂. The resulting material was then dried at 120° C. forsix hours and further calcined at 550° C. for six hours under flowingair. Palladium nitrate was added to the calcined material using anincipient wetness impregnation technique to achieve a target palladiumloading of 0.5 wt %. This material was then dried at 120° C. for sixhours and further calcined at 550° C. for six hours under flowing air.

Example 19

The catalyst systems referenced in Examples 14-18 were investigated forthe vapor-phase condensation of various oxygenates. The studies wereconducted using 8.5 mm and 21.2 mm internal diameter size stainlesssteel tube reactors as described in Example 4 and in the reactor systemsillustrated by FIGS. 8 and 10. Between 15 and 18 milliliters of catalystwas loaded into the smaller reactor, with between 50 and 70 millilitersof catalyst loaded into the larger reactor. In all cases the catalystwas reduced at 400° C. under flowing hydrogen prior to use.

The organic liquid phase was collected and analyzed as described inExample 5. Table 3 shows organic product yields and composition as afunction of operating conditions, feedstock composition, and the addedmetal component for the catalysts described in Examples 14-18 above.Greater than 100% reported organic phase yields stem from experimentaluncertainty in the measurement of process stream flow rates orcomposition. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

Experiments F and G demonstrate that product selectivity can be affectedby the choice of hydrogenation function, e.g. Pt or Pd. Paraffins wereproduced to a larger extent over the catalyst containing 1% platinumcompared to the catalyst containing 0.5% palladium. The later favoredthe production of mono-oxygenates, primarily ketones. Experiments H andI further reinforce this concept. Experiment H shows that condensedmono-oxygenate components can be obtained at high yield with isopropylalcohol as a feed, accounting for >97% of the organic product andcontaining >90% of the overall carbon at the reactor outlet. Byincreasing the reaction temperature and using copper to drive thehydrogenation reactions, the selectivity can be shifted to obtain asignificant yield of olefins (Experiment I). Experiments J, K and L showthat a number of other heterogeneous catalysts can be used to promotethe condensation of oxygenates followed by hydrogenation of the initialcondensation products. Experiments K and L show that as the temperatureis decreased from 300° C. to 250° C., the rate of condensation drops sothat the conversion to condensed products drops from 81 wt % to 18 wt %in the resulting organic phase.

TABLE 3 Vapor Phase Condensation of Oxygenates Over Basic CatalystsCatalyst 1% Pt/Cs Impregnated 0.5% 0.5% Siralox Pd/Ce Pd/Ce 1% Pt/ 0.5%Pd/ 0.5% Pd/ CuO/ZnO/ Silica- Modified Modified ZnO/Al2O3 ZnO/Al2O3ZnO/Al2O3 Al2O3 Alumina Silica Silica Experiment F G H I J K L Feed49.5% 2- 49.5% 2- 100% 100% 49.5% 2- 100% 100% Pentanone, Pentanone,Isopropyl Isopropyl Pentanone, Isopropyl Isopropyl 50.5% 2- 50.5% 2-Alcohol Alcohol 50.5% 2- Alcohol Alcohol Pentanol Pentanol Pentanol WHSVwt_(feed)/(wt_(catalyst) 1 1.5 1.5 2 1.1 1.9 1.9 hr) Added molH2/molfeed1 1 0 0 1 0 0 Hydrogen Temperature ° C. 375 375 300 375 325 300 250Pressure Psig 600 600 600 625 600 600 600 Organic Phase % of feed Yieldcarbon 75 99 95 55 107 74 98 Organic Phase Composition Breakdown C5−Hydrocarbons wt % 9.6 7.3 0.0 2.4 1.6 0.0 0.0 C5− Oxygenates wt % 6.220.9 1.9 14.6 75.8 18.5 81.8 Total Non- wt % 15.8 28.2 1.9 16.9 77.418.5 81.8 Condensed Components C6+ Paraffins wt % 49.5 18.9 0.3 1.0 0.020.1 0.2 C6+ Olefins wt % 4.6 0.0 0.0 15.9 0.0 0.0 0.0 Other C6+ wt %0.0 0.0 0.0 1.1 0.0 0.0 0.0 Hydrocarbons C6+ wt % 30.2 51.8 97.3 64.522.6 61.0 18.0 Monooxygenates Total Cond. wt % 84.2 70.7 97.6 82.5 22.681.1 18.2 Products

Condensation of Oxygenates Using Acid-Base Catalysts Example 20

A hydrotalcite catalyst was prepared from a commercially availablehydrotalcite support (ESM-350, ASM Catalysts, Baton Rouge, La.) bygrinding the material and passing through graduated screens to achieveparticles sizes larger than 60 mesh and less than 18 mesh. The materialwas then calcined in a quartz tube reactor at 450° C. for 6 hours underflowing nitrogen.

Example 21

Platinum was added to the hydrotalcite catalyst of Example 20 using anincipient wetness impregnation technique to achieve a final targetplatinum loading of 1 wt %. The platinum containing precursor washexachloroplatinic acid, H₂PtCl₆. The impregnated material was driedovernight under vacuum at 100° C. and subsequently calcined at 400° C.for 2 hours under flowing air.

Example 22

Platinum and tin were added to the hydrotalcite catalyst of Example 20using an incipient wetness impregnation technique to achieve a finaltarget loading of 1 wt % Pt and 0.2 wt % Sn. The platinum containingprecursor was hexachloroplatinic acid, H₂PtCl₆ while tin was derivedfrom tin chloride, SnCl₂*2H₂O. The impregnated material was driedovernight under vacuum at 100° C. and subsequently calcined at 450° C.for 8 hours under flowing nitrogen.

Example 23

A 5% magnesium oxide catalyst supported on granular zirconia wasprepared using an incipient wetness impregnation technique to achieve afinal target loading of 5 wt % Mg. Magnesium was added as magnesiumnitrate and dried overnight under vacuum at 100° C. and subsequentlycalcined at 450° C. for 8 hours under flowing air. An aqueous palladiumnitrate solution was added to the calcined material to achieve a targetpalladium loading of 0.5 wt % using an incipient wetness impregnationtechnique. The catalyst was dried a second time and calcined at 400° C.for six hours under flowing air.

Example 24

A zinc aluminate catalyst support was prepared by mixing zinc oxidepowder and alumina powder (Dispal 18N4-80, Sasol North America, Houston,Tex.) to a target ratio of 0.85 moles of ZnO to 1 mole of Al₂O₃. Dilutenitric acid was added at a level of 1 wt % HNO₃ to total solids. Thedough consistency was adjusted with water addition to form a workabledough suitable for extrusion and the mixture was extruded using alaboratory scale extruder. The extrudates were dried overnight undervacuum at 100° C. and subsequently calcined at 750° C. for 8 hours underflowing air. The material was then sized to 18 by 60 mesh. An aqueouspalladium nitrate solution was added to the calcined material to achievea target palladium loading of 0.5 wt % using an incipient wetnessimpregnation technique. This catalyst was then dried a second time andcalcined at 400° C. for six hours under flowing air.

Example 25

The catalyst systems referenced in Examples 21-24 were used to conductvapor-phase condensation reactions with various oxygenates. The studieswere conducted using 8.5 mm and 21.2 mm internal diameter size stainlesssteel tube reactors as described in Example 4 and reactor systems asillustrated in Examples 1 and 3. Between 15 and 18 milliliters ofcatalyst was loaded into the smaller reactor, with between 50 and 70milliliters of catalyst loaded into the larger reactor. In all cases thecatalyst was reduced at 400° C. under flowing hydrogen prior to use.

The organic liquid phase was collected and analyzed as described inExample 5. Table 4 shows the organic product yields and composition as afunction of operating conditions, feedstock composition, and the addedmetal component for the hydrotalcite catalysts described in Examples 21and 22 above. The data from the experiments show that a primarilyhydrocarbon product can be formed from acetone and isopropyl alcohol inthe absence of an added metal hydrogenation component. In Experiment M,the organic phase product contained primarily nine carbon methylsubstituted cyclohexenes, categorized as other C₆+ hydrocarbons in Table4. The addition of platinum (Experiment N) to this catalyst favored theformation of condensed mono-oxygenate products, mainly ketones andalcohols, and the formation of some paraffins as a result ofdeoxygenation of the ketones and alcohols. The selectivity was furthershifted in favor of condensed mono-oxygenates by attenuating theplatinum with tin and operating at a higher pressure (Experiment O).Experiments P, Q, R and S illustrate the impact of reaction temperaturefor the condensation of a mixed feed containing pentanol and pentanone.As the reaction temperature was raised from 300° C. to 375° C., agradual change in product composition became apparent, with theselectivity to condensed mono-oxygenates decreasing and the selectivityto condensed paraffins increasing as the temperature was raised.

Table 5 shows the impact of feedstock components and reactiontemperature on organic product yields and composition for the catalystsof Examples 23 and 24. Experiments T and U compare the condensation of2-pentanone and 2-methyltetrahydrofuran. Overall, the condensation of2-pentanone is faster than 2-methyltetrahydrofuran. Nonetheless, around30% of the tetrahydrofuran was converted to condensation products underthese conditions. Experiments 10 and 11 show the impact of reactiontemperature when using a pure isopropyl alcohol feed. At 300° C.(Experiment V), mono-oxygenated condensation products predominate, whileat 400° C. (Experiment W) a significant portion of the productsconsisted of hydrocarbons. Compared to other experiments listed inTables 4 and 5, Experiment W is notable in that the organic productcontained a higher level of olefins. The addition of valeric acid to thefeed (Experiment X) suppressed overall condensation rates and shiftedthe selectivity away from paraffins and towards other hydrocarbons,primarily substituted aryl compounds.

Greater than 100% reported organic phase yields stem from experimentaluncertainty in the measurement of process stream flow rates orcomposition. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

TABLE 4 Vapor Phase Condensation of Oxygenates Over HydrotalciteCatalysts Metal Function 1% Pt, 1% Pt, 1% Pt, 1% Pt, 1% Pt, None 1% Pt0.2% Sn 0.2% Sn 0.2% Sn 0.2% Sn 0.2% Sn Experiment M N O P Q R S Feed50% 50% 50% 49.5% 2- 49.5% 2- 49.5% 2- 49.5% 2- Isopropyl IsopropylIsopropyl Pentanone, Pentanone, Pentanone, Pentanone, Alcohol, Alcohol,Alcohol, 50.5% 2- 50.5% 2- 50.5% 2- 50.5% 2- 50% 50% 50% PentanolPentanol Pentanol Pentanol Acetone Acetone Acetone WHSV wt_(feed)/ 1.00.9 0.7 0.7 0.7 0.7 0.7 wt_(catalyst) hr Added mol_(H2)/mol_(feed) 0.5 00 1 1 1 1 Hydrogen Temperature ° C. 350 350 350 300 325 350 375 PressurePsig 100 100 600 600 600 600 600 Organic Phase % of feed 61 95 91 108104 108 85 Yield carbon Organic Phase Composition Breakdown C5− wt % 2.83.6 1.0 4.6 7.1 9.4 20.0 Hydrocarbons C5− Oxygenates wt % 11.9 16.0 5.841.9 21.4 13.7 8.8 Total Non- wt % 14.7 19.6 6.8 46.5 28.5 23.1 28.8Condensed Components C6+ Paraffins wt % 0.0 13.1 7.6 2.2 11.3 28.6 53.0C6+ Olefins wt % 5.1 1.2 1.0 0.0 0.2 0.0 0.0 Other C6+ wt % 72.8 0.0 0.00.0 0.0 0.0 0.0 Hydrocarbons C6+ wt % 5.7 54.3 80.4 51.4 60.1 47.8 18.2Monooxygenates Total wt % 83.5 68.6 89.0 53.6 71.6 76.5 71.2Condensation Products

TABLE 5 Vapor Phase Condensation of Oxygenates Over MagnesiumImpregnated Zirconia and Zinc Aluminate Catalysts Catalyst 0.5% Pd/ 0.5%Pd/ 0.5% Pd/ Zinc Zinc Zinc Aluminate Aluminate Aluminate 0.5% Pd/5%0.5% Pd/5% (0.85:1 (0.85:1 (0.85:1 Mg Zirconia Mg Zirconia ZnO:Al₂O₃)ZnO:Al₂O₃) ZnO:Al₂O₃) Experiment T U V W X Feed 100% 2- 100% 2-methyl-100% 100% 90% pentanone tetrahydrofuran Isopropyl Isopropyl Isopropylalcohol alcohol alcohol, 10% Valeric Acid WHSV wt_(feed)/(wt_(catalyst)hr) 2 2 1 1 1 Added Hydrogen mol_(H2)/mol_(feed) 1 1 0 0 0 Temperature °C. 400 400 300 400 400 Pressure psig 600 625 600 600 600 Organic PhaseYield % of feed carbon 85 76 104 58 53 Organic Phase CompositionBreakdown C5− Hydrocarbons wt % 7.4 4.0 0.4 2.8 2.0 C5− Oxygenates wt %21.4 66.5 5.2 6.9 17.3 Total Non-Condensed wt % 28.8 70.6 5.6 9.7 19.3Components C6+ Paraffins wt % 22.1 10.9 3.4 17.1 5.6 C6+ Olefins wt %0.0 2.8 0.0 23.8 13.6 Other C6+ Hydrocarbons wt % 1.3 0.3 0.0 8.1 19.8C6+Monooxygenates wt % 46.5 14.7 90.8 41.2 38.6 Total Cond. Products wt% 69.9 28.8 94.2 90.1 77.7

Base Condensation of Oxygenates Followed by Deoxygenation Example 26

A zinc aluminate catalyst support was prepared similar to that inExample 13 except that the amount of zinc oxide was reduced to target aratio of 0.85 moles of ZnO to 1 mole of Al₂O₃.

Example 27

Hexachloroplatinic acid was added to the calcined material of Example 26using an incipient wetness impregnation technique to achieve a targetplatinum loading of 1.0 wt %. The catalyst was dried overnight undervacuum at 100° C. and calcined at 400° C. under flowing air.

Example 28

The catalyst systems referenced in Examples 27 and 15 were investigatedfor the vapor-phase condensation of various oxygenates and subsequentconversion to hydrocarbons. The studies were conducted using 21.2 mminternal diameter size stainless steel tube reactors as described inExample 4, and reactor systems as illustrated by Examples 2 and 3.Approximately 100 milliliters of each catalyst was loaded into twoseparate reactors. The two reactors were arranged so that the effluentof the first reactor flowed into the second reactor. The first reactorcontained the catalyst of Example 15 and the second reactor containedthe catalyst of Example 27. The catalyst was reduced at 400° C. underflowing hydrogen prior to use. In all cases, hydrogen was combined withthe feed prior to entering the reactor.

Products were separated and analyzed as described in Example 5. Table 6shows organic product yields and composition as a function of operatingconditions and feedstock composition obtained from the consecutivereactions. Non-condensed components are those components that do notrequire the formation of new carbon-carbon bonds to be produced from thegiven feed. For simplicity, all compounds containing five or fewercarbon atoms are considered to be non-condensed components. Totalcondensation products are those compounds containing six or more carbonatoms, which require the formation of new carbon-carbon bonds to beformed from the given feedstocks.

Experiments AA, BB, CC, and DD demonstrate that various oxygenates canbe employed in the consecutive condensation and deoxygenation reactionsto yield a product containing primarily C₆₊ alkanes. The productscontain a larger fraction of alkanes and low levels of oxygenatedcompounds compared to the results shown in Table 3. This demonstratesthat the use of catalysts with different functionalities (i.e. abasic+hydrogenation catalyst in a first reactor followed byacid+basic+hydrogenation catalyst in the second reactor) can be moreeffective for the production of hydrocarbons from oxygenated compoundsthan the use of a catalyst that contains only basic and hydrogenationfunctionality. In Experiment EE, the organic product produced inExperiments AA through DD was recycled through the reaction system.After this treatment, the final product contained primarily alkanes withonly traces of oxygen containing components. The hydrocarbons thusproduced would be valuable for use as liquid fuels such as gasoline,diesel, and jet fuel.

TABLE 6 Vapor Phase Condensation and Deoxygenation of OxygenatesExperiment AA BB CC DD EE Feed 100% 50% 100% 2- 50% Organic IsopropylIsopropyl Pentanone + Acetone + Phase Alcohol Alcohol + 50% 2- From 50%2- Pentanone AA-DD Pentanone WHSV wt_(feed)/ 1.9 2.2 2.1 2.0 2.0(wt_(catalyst) hr) Added mol_(H2)/mol_(feed) 1.5 1.7 2 2 >2 HydrogenReactor 1 ° C. 300 300 300 300 325 Temperature Reactor 2 ° C. 350 375375 375 375 Temperature Pressure psig 625 625 625 625 625 Organic Phase% of feed 81 76 80 93 87 Yield carbon Product Composition Breakdown C5−% of feed 8 11 15 33 15 Hydrocarbons carbon C5− Oxygenates % of feed 3 22 4 0 carbon Total Non- % of feed 11 13 18 37 15 Condensed carbonComponents C6+ Alkanes % of feed 71 71 65 56 74 carbon C6+ Alkenes % offeed 0 0 0 0 0 carbon Other C₆₊ % of feed 0 0 0 0 0 Hydrocarbons carbonC₆₊ % of feed 6 5 3 2 0 Monooxygenates carbon Total Products % of feed77 76 68 58 74 (Condensation) carbon

Product Fractionation Example 29

The material of Experiment EE of Example 28 was collected and subjectedto a distillation step. The distillation was conducted at atmosphericpressure using a simple, single stage laboratory batch distillationapparatus. 2.950 liters of liquid product was added to a heated roundbottomed flask which acted at the reboiler at the beginning of theexperiment. The overhead product was condensed and segregated intoseparate samples based on the temperature of the vapor phase inequilibrium with the boiling liquid, with an analysis of the fractionscompleted as described in Example 5. The carbon number distribution ofthe product fractions is shown in Table 7. All fractions containedprimarily alkanes.

The fractions recovered with a boiling point less than 150° C. containalkanes mainly in the C₅₋₁₀ range and would be suitable as a gasolineblending component. The higher boiling point range materials could bepotentially useful for incorporation into distillate fuels, kerosene anddiesel.

Example 30

The distilled product boiling in the range of 150° C. to 250° C. wasanalyzed for suitability as a Jet Fuel by a commercial testing service(Intertek Testing Services, Illinois) according to ASTM testing methodD1655. The sample passed all required specifications with the exceptionof the flash point and density specifications. It is probable that theflash point specification could be met through adoption of improvedproduct distillation, while the low density may be attributed to thehigh levels of alkanes in the sample.

TABLE 7 Results from Distillation of the Product of Example 30 Less 100150 Greater Boiling Starting than to to than Range ° C. Material 100 150250 250 Volume milliliters 2950 750 750 1300 180 Recovered Total wt %99.8 100.0 100.0 99.4 91.4 Alkanes Carbon Number Breakdown by SpeciesCarbon Number C₄₋ wt % 0.2 0.4 C₅₋₉ wt % 52.6 96.0 78.1 13.7 C₁₀₋₁₄ wt %41.3 3.6 21.9 78.3 29.9 C₁₅₊ wt % 5.7 7.4 61.5

Production of C5+Compounds from Glycerol Using a Single Catalytic SystemExample 31

A bimetallic catalyst system containing platinum and rhenium (5 wt %platinum with a molar ratio of Pt:Re of 1:2.5) supported on activatedcarbon (Calgon UU 60×120 mesh carbon) was prepared using incipientwetness techniques. Activated carbon was added slowly to a 30% hydrogenperoxide solution. After addition of the carbon was completed, themixture was left overnight. The aqueous phase was decanted and thecarbon was washed three times with of deionized water, and then driedunder vacuum at 100° C. An aqueous solution, with a volume equal toincipient wetness volume for the carbon to be impregnated, 10.4 mL, andcontaining dihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar,39.85% Pt) and perrhemic acid solution (Alfa Aesar, 76.41% HReO₄) wasapplied drop wise, while stirring, to hydrogen peroxide functionalizedcarbon. The wetted carbon was dried at 100° C. under vacuum.

Example 32

104.4 grams of the 1:2.5 Pt/Re catalyst were loaded into a 63.5 cm longreactor tube as described in Example 4 and Example 1, except that thetemperature profile was controlled by heat exchange with a hot airstream provided by a blower and heater as illustrated in FIG. 7. Thecatalyst was reduced with flowing hydrogen at 350° C. for two hoursbefore liquid feed was introduced to the catalyst bed. A 50 wt %glycerol (Colgate Palmolive USP Grade) containing about 20 ppm sulfatein water solution was fed downflow across the reactor after beingpreheated to 182° C. at a weight hourly space velocity of 0.97 grams ofglycerol per gram of catalyst per hour. Hot air was fed upflow throughthe annular space at 409° C. The axial temperature profile within thecenter of the catalyst bed was measured using a sliding thermocouple asshown in Example 4, and is illustrated in FIG. 13. The separatorpressure was maintained at 600 psig. The effluent from the reactor wascooled down with a water cooled condenser and separated in a three-phaseseparator. The gas-phase products were analyzed with a gas chromatographthat allowed the analysis of hydrogen, carbon dioxide, methane, ethane,propane, butane, pentane, and hexane. An organic phase was collected,weighed, and sent to Southwest Research Institute (San Antonio, Tex.)for gasoline analysis. The aqueous-phase was collected and weighed, andthen analyzed using both a GCMS as well as GC-FID. In this system, therewas complete conversion of the glycerol. Table 8 below shows the yieldsof hydrogen as well as the yields of carbon containing productcompounds.

TABLE 8 Yields for the Conversion of Glycerol from Example 32 Productsmoles of H2/mole of glycerol feed 1.03 % Carbon/Carbon in Feed CO2 31.79Methane 7.35 Ethane 7.28 Propane 5.25 Butane 0.56 Pentane 1.40 Hexane2.05 C7-C13 Normal 0.87 C4-C13 Iso 2.87 C6-C12 Aromatic 3.87 C8-C11Naphthalene/Napthenes 1.89 C5-C10 Olefins 5.67 C4-C6 OxygenatedCompounds in 1.86 Organic Phase Ethanol in Aqueous Phase 0.39 AceticAcid in Aqueous Phase 1.33 Acetone in Aqueous Phase 13.19 Propanoic Acidin Aqueous Phase 4.69 Propylene Glycol in Aqueous Phase 2.79 1-Propanolin Aqueous Phase 1.71 Isopropyl Alcohol in Aqueous Phase 1.28 C4/C5/C6in Aqueous Phase 2.20

Production of C5+Compounds from Sugar Alcohols Example 33

Experiments were conducted with aqueous solutions of oxygenatedhydrocarbons (e.g., 50 wt. % glycerol/water mixture or 50 wt %sorbitol/water mixture) introduced in to the reactor system ofExample 1. The feedstock was further modified by the addition of K₂SO₄at various concentrations (1, 20, or 50 ppm).

Example 34

A total of 10.61 grams of the 1:2.5 Pt/Re catalyst were loaded into the8.5 mm stainless steel reactor tube described in Example 4. The catalystwas reduced with flowing hydrogen at 350° C. for two hours before liquidfeed was introduced to the catalyst bed. A 50 wt % glycerol solutioncontaining about 1 ppm sulfate in water solution was fed downflow acrossthe reactor at a WHSV of 1.24 grams of glycerol per gram of catalyst perhour. Subsequent tests were performed with 20 ppm and 50 ppm sulfateadded as K₂SO₄. The block heaters were controlled at 260° C. and theseparator pressure was maintained at 600 psig.

An organic phase was collected from the separated, weighed, and analyzedwith a GC-MS as described in Example 5. Table 9 below shows the yieldsof hydrogen as well as the yields of carbon containing product compoundswith the different amounts of sulfate added to the system. In thissystem, there was complete conversion of the glycerol. The table showsthat a liquid organic phase was generated with the addition of sulfategreater than 20 ppm.

TABLE 9 Yields of Hydrogen and Carbon Containing Products from Example34 K₂SO₄ loading Sulfate 1 20 50 Block 1 Temperature (° C.) (FIG. 8,10a) 260 260 260 Block 2 Temperature (° C.) (FIG. 8, 10b) 260 260 260Block 3 Temperature (° C.) (FIG. 8, 10c) 260 260 260 Block 4 Temperature(° C.) (FIG. 8, 10d) 260 260 260 H₂ produced/mole of glycerol feed 1.671.26 0.72 % Carbon/Carbon in Feed CO₂ 48.9% 44.4% 27.4% CH₄ 14.5% 12.7%6.1% C₂H₆ 18.9% 16.0% 6.0% C₃H₈ 9.4% 7.4% 4.8% C₄H₁₀ 0.6% 0.7% 0.2%C₅H₁₂ 1.0% 1.0% 0.3% C₆H₁₄ 1.1% 0.7% 0.1% C₆ ⁺ Hydrocarbons in OrganicPhase 0.0% 0.4% 5.4% C₂-C₆ Oxygenates in Organic Phase 0.0% 1.7% 7.9%C₂-C₆ Oxygenates in Aqueous Phase 6.9% 13.3% 42.6%

Example 35

A total of 10.61 grams of the 1:2.5 Pt/Re catalyst were loaded into the8.5 mm stainless steel reactor tube described in Example 4 and thereactor system illustrated in Example 1. The catalyst was reduced withflowing hydrogen at 350° C. for two hours before liquid feed wasintroduced to the catalyst bed. A 50 wt % glycerol solution containingeither 1 ppm or 20 ppm sulfate in water was fed downflow across thereactor at a WHSV of 1.24 grams of glycerol per gram of catalyst perhour. The block heaters were controlled such that the first 10.1 cm ofthe reactor was held at 260° C., the second 10.1 cm of the reactor wasat approximate 306° C., the next 10.1 cm of the reactor was atapproximately 355° C., and the last 10.1 cm of the reactor at 400° C.The separator pressure was maintained at 600 psig.

The effluent from the reactor was cooled down with a water cooledcondenser, separated in a three-phase separator, and then analyzed asdescribed in Example 5. In this system, there was complete conversion ofthe glycerol. Table 10 below shows the yields of hydrogen as well as theyields of carbon containing product compounds.

TABLE 10 Yields of Hydrogen and Carbon Containing Products from Example35 K₂SO₄ loading Sulfate 1 20 Block 1 Temperature (° C.) 260 260 Block 2Temperature (° C.) 307 305 Block 3 Temperature (° C.) 354 356 Block 4Temperature (° C.) 400 400 H2 produced/mole of glycerol feed 1.01 0.83 %Carbon/Carbon in Feed CO₂ 42.8% 41.7% CH₄ 15.7% 16.1% C₂H₆ 15.8% 11.9%C₃H₈ 19.9% 18.2% C₄H₁₀ 1.8% 3.0% C₅H₁₂ 2.3% 3.4% C₆H₁₄ 1.0% 1.7% C₆ ⁺Hydrocarbons in Organic Phase 0.0% 1.1% C₂-C₆ Oxygenates in OrganicPhase 0.0% 0.7% C₂-C₆ Oxygenates in Aqueous Phase 0.2% 0.1%

Example 36

A bimetallic catalyst system containing platinum and rhenium (5 wt %platinum with a molar ratio of Pt:Re of 1:5) supported on activatedcarbon (Calgon UU 60×120 mesh carbon) was prepared using an incipientwetness technique. Activated carbon was added slowly to a 30% hydrogenperoxide solution. After addition of the carbon was completed, themixture was left overnight. The aqueous phase was decanted and thecarbon was washed three times with deionized water, and then dried undervacuum at 100° C. An aqueous solution, with a volume equal to theincipient wetness volume for the carbon to be impregnated and containingdihydrogen hexachloroplatinate (IV) hexahydrate (Alfa Aesar, 39.85% Pt)and perrhemic acid solution (Alfa Aesar, 76.41% HReO₄) was applied dropwise, while stirring, to hydrogen peroxide functionalized carbon. Thewetted carbon was then dried at 100° C. under vacuum.

Example 37

11.97 grams of the 1:5 Pt/Re catalyst described in Example 36 wereloaded into the 8.5 mm diameter stainless steel tube as described inExample 4 and the reactor system illustrated in Example 1. The catalystwas reduced with flowing hydrogen at 350° C. for two hours before liquidfeed was introduced to the catalyst bed. A 57.2 wt % sorbitol solutioncontaining 0 ppm sulfate in water solution was fed downflow across thereactor at a WHSV of 1.20 grams of sorbitol per gram of catalyst perhour. The block heaters were controlled such that the first 10.1 cm ofthe reactor was held at 260° C., the second 10.1 cm of the reactor wasat 260° C., the next 10.1 cm of the reactor was at 360° C., and the last10.1 cm of the reactor at 410° C. The separator pressure was maintainedat 600 psig. The effluent from the reactor was cooled down with a watercooled condenser and separated in a three-phase separator. The productfractions were analyzed as described in Example 5. In addition, theorganic phase was collected, separated, and weighed, with a sample sentto Southwest Research Institute (San Antonio, Tex.) for gasolineanalysis. In this system, there was complete conversion of the glycerol.Table 11 below shows the yields of hydrogen as well as the yields ofcarbon containing product compounds.

TABLE 11 Yields of Hydrogen and Carbon Containing Products from Example37 Block 1 Temperature (° C.) (FIG. 8, 10a) 260 Block 2 Temperature (°C.) (FIG. 8, 10b) 260 Block 3 Temperature (° C.) (FIG. 8, 10c) 360 Block4 Temperature (° C.) (FIG. 8, 10d) 410 Products moles of H2/mole ofSorbitol feed 1.36 % Carbon/Carbon in Feed CO2 44.37 Methane 9.24 Ethane8.25 Propane 11.74 Butane 6.53 Pentane 5.66 Hexane 3.79 C7-C13 Normal0.08 C4-C13 Isoparaffin 0.99 C6-C12 Aromatic 2.45 C8-C11Naphthalene/Napthenes 0.93 C5-C10 Olefins 0.45 C4-C6 OxygenatedCompounds in Organic Phase 1.68 Oxygenates in Aqueous Phase 3.83

Conversion of Oxygenates to C5+Compounds Using Acidic Catalysts Example38

An aqueous 1.0 molar lanthanum nitrate solution was prepared and addedto H-mordenite extrudates (BASF 712A-5-2641-1) for a target of 3 weight% La on the catalyst after the subsequent decomposition of the metalprecursor. The La solution was mixed briefly with the catalyst and thensoaked at 80° C. for 6 hours. The excess liquid was then removed and thecatalyst rinsed with deionized water. The catalyst was then dried in avacuum oven and calcined in air at 550° C. Following this, the catalystwas ground and sieved to restrict the particles sizes to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen.

Example 39

Deionized water was added to H-mordenite extrudates (BASF 712A-5-2641-1,with particle sizes restricted to those that were maintained on a 60mesh screen after passing through an 18 mesh screen) until extra watercovered the support. An aqueous 0.36 molar nickel nitrate solution wasthen added to the wet support to target 1 weight % Ni afterdecomposition of the metal precursor. The catalyst was mixed briefly andleft to soak for 48 hours. The catalyst was then dried in a vacuum ovenand calcined in air at 400° C.

Example 40

An aqueous 1.0 molar europium chloride solution was prepared and addedto H-Mordenite (BASF 712A-5-2641-1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) for a target of 3 weight % Eu on the catalyst after thesubsequent decomposition of the metal precursors. The Eu solution wasmixed briefly with the catalyst and then soaked at 80° C. for 6 hours.The excess liquid was then removed and the catalyst rinsed withdeionized water. The catalyst was then dried in a vacuum oven andcalcined in air at 550° C. Following this the catalyst was ground andsieved to restrict the particles sizes to those that were maintained ona 60 mesh screen after passing through an 18 mesh screen.

Example 41

H-Beta zeolite extrudates (1.6 mm diameter extrudates) were ground andsieved to restrict the particle sizes to those that were maintained on a60 mesh screen after passing through an 18 mesh screen. An aqueousgallium nitrate solution was added by incipient wetness to target 1.2weight % Ga on the catalyst after decomposition of the metal precursor.The catalyst was then dried in a vacuum oven and calcined in air at 400°C.

Example 42

Phosphoric acid was diluted with deionized water and added by incipientwetness to a Davicat SiO₂/Al₂O₃ support (Grace-Davis, with particlesizes restricted to those that were maintained on a 60 mesh screen afterpassing through an 18 mesh screen) to target 5 weight % phosphorous onthe catalyst. The catalyst was then dried in a vacuum oven overnight andsubsequently calcined in a stream of flowing air at 500° C.

Example 43

An aqueous nickel nitrate solution was added to an alumina bound ZSM-5zeolite preparation (SiO₂:Al₂O₃ 30:1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) using an incipient wetness technique to target a nickelloading of 1.0 weight %. The preparation was dried overnight in a vacuumoven and subsequently calcined in a stream of flowing air at 400° C.

Example 44

An aqueous gallium nitrate solution was added to an alumina bound ZSM-5zeolite preparation (SiO₂:Al₂O₃ 80:1, with particle sizes restricted tothose that were maintained on a 60 mesh screen after passing through an18 mesh screen) using an incipient wetness technique to target a galliumloading of 1.2 weight %. The preparation was dried overnight in a vacuumoven and subsequently calcined in a stream of flowing air at 400° C.

Example 45

Catalyst systems produced using the methods of Examples 38 to 44 wereinvestigated for the vapor-phase condensation of various oxygenates at atemperature from 325° C. to 375° C. and a total pressure between 200psig and 625 psig, and with WHSVs ranging from 1.9 to 42.8. In theseinvestigations, two different size reactors were used; 15 and 18milliliters of catalyst were loaded into a 8.5 mm internal diameterstainless steel tube reactor or between 50 and 70 milliliters ofcatalyst were loaded into a 21.2 mm stainless steel tube reactor(Example 4). The reaction process flow was as described in Example 1 orExample 3 depending on the feedstock, with an analysis completed asdescribed in Example 5.

Operating conditions and results from these experiments are shown inTable 12. Where feed compositions add up to less than 100%, the balancewas water. As these results show, a variety of oxygenates, includingalcohols and ketones, both 3 carbon and 5 carbon, are substrates whichmay be converted to C₅+ hydrocarbons across a broad range of conditions.Zeolites are particularly useful in these conversions, as shown byexperiments FF, GG, HH, II, JJ, LL, and MM. Experiments FF, GG, HH, II,and JJ show that the main products of alcohol conversion acrossmordenite and beta zeolites were olefinic condensation products. Thephosphorous impregnated silica alumina catalyst, experiment KK,demonstrated a similar product selectivity profile. In contrast, theZSM-5 based catalysts, Experiments LL and MM, produced significantfractions of aromatic and paraffinic components.

TABLE 12 Vapor Phase Condensation of Oxygenates Over Acid CatalystsCatalyst 5% Ni/30:1 Ga/80:1 Phosphorous/ SiO2:Al2O3 SiO2:Al2O3La/mordenite Ni/mordenite Eu/mordenite Eu/mordenite Ga/BetaSilica-Alumina ZSM-5 ZSM-5 Experiment FF GG HH II JJ KK LL MM Feed 50%2- 50% 59% 2- 50% 50% 90% 50% 89.6% pentanol isopropyl pentanolisopropyl isopropyl isopropyl isopropyl Acetone alcohol alcohol alcoholalcohol alcohol WHSV wt_(feed)/ 1.9 2.1 2.2 1.9 3.1 2.7 42.8 2.1wt_(catalyst) hr) Reactor ° C. 325 350 325 375 375 375 375 375Temperature Pressure psig 625 625 600 600 600 600 200 625 Reactor OutletYield Distribution C⁴⁻ Alkanes wt% of feed 2.9 0.7 3.9 3.6 1.2 1.6 9.67.0 carbon C⁴⁻ Olefins wt% of feed 19.5 47.7 11.3 32.9 32.5 73.5 10.80.5 Total C⁴⁻ carbon Hydrocarbons wt% of feed 22.3 48.4 15.3 36.5 33.775.1 20.5 7.5 carbon C₅₊ Paraffins wt% of feed 6.6 0.8 16.9 3.1 4.3 1.929.6 8.5 carbon C₅₊ Olefins wt% of feed 56.2 46.9 43.1 56.6 52.0 18.421.7 0.1 carbon Naphthenes wt% of feed 0.0 2.5 1.5 5.6 3.2 3.4 2.7 1.0carbon Aromatics wt% of feed 0.0 0.0 1.4 0.0 2.0 0.0 18.0 79.1 carbonOther C₅₊ wt% of feed 0.8 0.1 5.7 1.5 0.2 0.0 7.1 0.0 Hydrocabons carbonTotal C₅₊ wt% of feed 63.6 50.3 68.6 66.7 61.8 23.7 79.2 88.6Hydrocarbons carbon

Production of C5+Compounds from Oxygenated Hydrocarbons Example 46

A catalyst preparation technique identical to that of Example 44 wasfollowed with the exception that the alumina bound ZSM-5 material had aSiO₂:Al₂O₃ ratio of 30:1.

Example 47

A catalyst produced using the method of Example 46 was investigated forthe vapor-phase condensation of a mixture of oxygenates at 375° C. and200 psig. In this investigation, 11.3 grams of catalyst were loaded intoa 8.5 mm internal diameter stainless steel tube reactor as described inExample 4. The reaction process flow was as described in Example 3. Theoxygenate mix included, by weight, 25% 2-pentanone, 20% 3-pentanone, 20%2-pentanol, 10% isopropyl alcohol, 10% valeric acid, 5% 2-methyltetrahydrofuran. This mixture was added using one pump in the Example 3reactor system while the second pump added water so that the totalcombined feed contained 60 weight % water and 40 weight % of mixedoxygenates.

The process was monitored for a period of 128 hours, with samplesperiodically removed from the system to analyze the process performance.Each analysis was completed as described in Example 5. FIG. 15 shows thefraction of feed carbon that exited the reactor system as C₅₊ compoundsas a function of time. FIG. 16 shows the fraction of feed carbon thatexited the reactor system as an aromatic hydrocarbon as a function oftime. FIG. 14 shows the fraction of feed carbon that exited the reactorsystem as oxygenates as a function of time.

As FIGS. 14, 15 and 16 show, the catalyst system is able to operate forextended periods of time with an oxygenate mix that contains a mixtureof oxygenates, including alcohols, ketones, an acid, and atetrahydrofuran. Over time the production of C₅+ compounds remainsrelatively stable, while the amount of aromatic hydrocarbons present inthe product drops and the breakthrough of oxygenated compounds increases(FIG. 14). It is believed that the catalyst deactivation is primarilydue to the accumulation of carbonaceous deposits limiting theaccessibility of the reactants to the active sites.

Example 48

An aqueous solution of hexachloroplatinic acid and perrhenic acid wasadded to a carbon catalyst support (OLC-AW, Calgon, with particle sizesrestricted to those that were maintained on a 50 mesh screen afterpassing through an 120 mesh screen) using an incipient wetness techniqueto target a platinum loading of 1.8% and a rhenium loading of 6.3% onthe catalyst after subsequent decomposition of the metal precursors. Thepreparation was dried overnight in a vacuum oven and subsequentlyreduced in a stream of flowing hydrogen at 400° C. After being reducedthe catalyst was stored in a nitrogen atmosphere until ready for use.

Example 49

A catalyst preparation technique identical to that of Example 44 wasfollowed with the exception that the alumina bound ZSM-5 material had aSiO₂:Al₂O₃ ratio of 150:1.

Example 50

Hexachloroplatinic acid and perrhenic acid dissolved in water were addedto a monoclinic zirconia catalyst support (NorPro Saint Gobain, productcode SZ31164, with particle sizes restricted to those that weremaintained on a 60 mesh screen after passing through an 18 mesh screen)using an incipient wetness technique to target a platinum loading of1.8% and a rhenium loading of 6.3% on the catalyst after subsequentdecomposition of the metal precursors. The preparation was driedovernight in a vacuum oven and subsequently calcined in a stream offlowing air at 400° C.

Example 51

The same procedure used for preparing the catalyst of Example 50 wasfollowed with the exception that the target rhenium loading was 1.8%.

Example 52

An 80:1 SiO₂:Al₂O₃ ratio ZSM-5 zeolite (Zeolyst International, CBV 8014)was mixed with a 1:1 molar ratio of ZnO and Al₂O₃ powders so that theZnO and Al₂O₃ (Dispal 18N4-80, Sasol North America, Houston, Tex.)combined comprised 30 weight % of the total solids. Dilute nitric acidwas added at a level of 2 weight % HNO₃ to the combined ZnO and Al₂O₃.The dough consistency was adjusted with water addition to form aworkable dough suitable for extrusion and the mixture was extruded usinga laboratory scale extruder. The extrudates were dried overnight undervacuum at 100° C. and subsequently calcined at 600° C. under flowingair.

Example 53

An aqueous solution of gallium nitrate was added to the material ofExample 52, with particle sizes restricted to those that were maintainedon a 60 mesh screen after passing through an 18 mesh screen, using anincipient wetness technique to target a gallium loading of 1.2 weight %.The preparation was dried overnight in a vacuum oven and subsequentlycalcined in a stream of flowing hydrogen at 400° C.

Example 54

An aqueous solution of nickel nitrate was added to the material ofExample 52, with particle sizes restricted to those that were maintainedon a 60 mesh screen after passing through an 18 mesh screen, using anincipient wetness technique to target a nickel loading of 1.0 weight %.The preparation was dried overnight in a vacuum oven and subsequentlycalcined in a stream of flowing hydrogen at 400° C.

Example 55

The catalyst systems referenced in Examples 6, 46, 48, 49, 51, 53, and54 were investigated for the conversion of glycerol, sorbitol, sucrose,and xylose to hydrocarbons using the reactor configuration described inExample 2. The studies were conducted using two 21.2 mm internaldiameter stainless steel tube reactors shown in Example 4, with ananalysis completed as described in Example 5. Tungstated zirconia(NorPro-Saint Gobain, product code SZ61143, with particle sizesrestricted to those that were maintained on a 60 mesh screen afterpassing through an 18 mesh screen) was placed on top of the condensationcatalyst installed in the second reactor to provide for a zone forvaporization of the first reactor effluent prior to entering thecondensation catalyst.

Table 13 shows the results of these investigations. For Experiment NN(38% Sucrose+7% Xylose), a stream of hydrogen with a targeted flow rateequal to 3 times the moles of sucrose plus 1.5 times the moles of xylosewas combined with the feed prior to entering the reactor. The otherexperiments were conducted without externally supplied hydrogen. Heatersexternal to the reactor, shown in FIG. 9 as 10 a, 10 b, 10 c, 10 d, 23a, 23 b, 23 c, and 23 d, were used to maintain the reactor walltemperatures, as indicated in Table 13. The hydrocarbon products ofthese studies, disclosed in Table 13, were grouped into a C⁴⁻ fraction,which are predominately present in the gas phase at ambient temperatureand pressure, and a C₅₊ fraction, which are generally suitable forincorporation into liquid fuels. The results show that a variety ofsugars and polyhydric alcohols may be readily converted to C₅₊hydrocarbons by the processes described here. The products containedmainly paraffin and aromatic constituents. The breakdown of paraffinsand aromatics within this sample is shown in FIG. 17.

TABLE 13 Conversion of Sugars and Polyhydric Alcohols to C5+Hydrocarbons Experiment NN OO PP QQ Catalyst Descriptions HydrogenationExample 6  None None None APR/Deoxygenation Example 48 Example 51Example 51 Example 50 Condensation Example 49 Example 53 Example 46Example 54 Catalyst Loadings Hydrogenation grams 10 — — —APR/Deoxygenation grams 40 52 60 60 Tungstated Zirconia grams 71 60 ~6058 Condensation grams 62 60 60 60 Heater Block Temperature Ranges, Inletof Catalayst Bed-Outlet of Catalyst Bed Hydrogenation ° C. 100-150 — — —APR/Deoxygenation ° C. 245-265 250-270 335-365 275-285 TungstatedZirconia ° C. 250-375 370-370 395-375 395-375 Condensation ° C. 375-375385-385 375-375 375-375 Pressures First Reactor Outlet psig 625 625 625625 2nd Reactor Outlet psig 625 350 250 350 Feed 38% 50% 50% 50%Sucrose + 7% Glycerol Glycerol Sorbitol Xylose Hydrogen mol/mol feed−2.85 0.73 0.57 0.50 production WHSV wt_(feed)/(wt_(catalyst) 1.6 1.92.0 2.0 hr) Reactor Outlet Yield Distribution C⁴⁻ Alkanes wt % of feed21.2 26.9 8.1 13.0 carbon C⁴⁻ Olefins wt % of feed 1.1 1.4 1.3 5.2carbon Total C⁴⁻ wt % of feed 22.3 28.3 9.4 18.1 Hydrocarbons carbon C₅₊Paraffins wt % of feed 20.0 7.9 9.5 11.3 carbon C₅₊ Olefins wt % of feed0.8 1.9 1.2 7.8 carbon Naphthenes wt % of feed 1.9 1.4 1.6 1.2 carbonAromatics wt % of feed 25.0 17.8 48.4 22.3 carbon Other C₅₊ wt % of feed0.0 1.1 0.2 3.4 Hydrocabons carbon Total C₅₊ wt % of feed 47.7 30.1 61.046.1 Hydrocarbons carbon

Example 56

The process described in Example 55 and exemplified by Experiment QQ inTable 13 was operated for a period of more than 400 hours. After aninitial period of time in operation, the conversion to aromaticcomponents and the yield of hydrocarbons dropped, shown in FIGS. 18 and19 as Cycle 1. In FIG. 18, the heating value of C₅₊ hydrocarbons presentat the outlet of the second reactor, as a percentage of the heatingvalue of the feed, is shown. In FIG. 19, the carbon present as aromatichydrocarbons at the outlet of the second reactor is shown as apercentage of the carbon present in the feed. After approximately 120hours on stream, the second reactor was bypassed while the first reactorcontinued operating. An oxidative regeneration of the catalyst in thesecond reactor was then performed. During the regeneration, a flow ofnitrogen and air was initiated so that the target oxygen concentrationat the second reactor inlet was 1 mol %. The second reactor blocktemperatures were then raised to 500° C. and the flow of nitrogen andoxygen continued until carbon dioxide was no longer detected at thesecond reactor outlet. The oxygen concentration was then raised to atarget level of 5 mol %. This flow was continued until carbon dioxidewas no longer detected at the second reactor outlet. At this time theoxygen flow was discontinued while the nitrogen flow continued. Thesecond reactor block temperatures were then reduced to 400° C. while thecomposition of the gas flowing through the catalyst bed was changed tohydrogen. The second reactor block temperatures were then adjusted tothose shown for Experiment QQ in Table 13. The second reactor was thenplaced back on line, targeting the conditions shown for Experiment QQ inTable 13. The second reactor was then subjected to multiple cycles ofoperation and regeneration, with the results for the period of time inoperation shown in FIGS. 18 and 19. As these results show, theregeneration of the condensation catalyst resulted in a restoration ofactivity, consistent with the theory that deposition of carbonaceousmaterials were the main cause of a drop in catalyst performance overtime. Furthermore, the results show that the condensation catalyst maybe regenerated multiple times without a significant loss of performance.

The invention claimed is:
 1. A method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons, the method comprising: reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a weight hourly space velocity of at least 0.6 h⁻¹, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising: a vapor phase; an organic phase comprising linear or cyclic mono-oxygenated hydrocarbons having from 4 to 6 carbon atoms and selected from the group consisting of alcohols, ketones, carboxylic acids, and 5- and 6-membered oxygen-containing heterocycles, and wherein molar carbon distribution for conversion of the water soluble oxygenated hydrocarbon reactant into the organic phase is at least 43%; and an aqueous phase; and then subjecting the organic phase to a carbon-carbon bond-forming reaction, in the presence of a metal-containing catalyst, to yield C₈-C₁₂ compounds.
 2. The method of claim 1, further comprising subjecting the C₈-C₁₂ compounds to a hydrodeoxygenation reaction to yield C₈-C₁₂ alkanes.
 3. A method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons, the method comprising: reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a weight hourly space velocity of at least 0.6 h⁻¹, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising: a vapor phase; an organic phase comprising linear or cyclic mono-oxygenated hydrocarbons having from 4 to 6 carbon atoms and selected from the group consisting of alcohols, ketones, carboxylic acids, and 5- and 6-membered oxygen-containing heterocycles, and wherein molar carbon distribution for conversion of the water soluble oxygenated hydrocarbon reactant into the organic phase is at least 43%; and an aqueous phase; and then subjecting the organic phase to an aldol condensation reaction to yield compounds having more carbon atoms than the reactant.
 4. A method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons, the method comprising: reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a weight hourly space velocity of at least 0.6 h⁻¹, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising: a vapor phase; an organic phase comprising linear or cyclic mono-oxygenated hydrocarbons having from 4 to 6 carbon atoms and selected from the group consisting of alcohols, ketones, carboxylic acids, and 5- and 6-membered oxygen-containing heterocycles, and wherein molar carbon distribution for conversion of the water soluble oxygenated hydrocarbon reactant into the organic phase is at least 43%; and an aqueous phase; and then hydrogenating the organic phase, wherein ketones present in the organic phase are reduced to alcohols; and then dehydrating the alcohols to yield alkenes.
 5. The method of claim 4, further comprising: subjecting the alkenes to alkylation reaction over an acid catalyst to form carbon-carbon bonds, thereby yielding longer chain alkenes.
 6. A method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons, the method comprising: reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a weight hourly space velocity of at least 0.6 h⁻¹, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising: a vapor phase; an organic phase comprising linear or cyclic mono-oxygenated hydrocarbons having from 4 to 6 carbon atoms and selected from the group consisting of alcohols, ketones, carboxylic acids, and 5- and 6-membered oxygen-containing heterocycles, and wherein molar carbon distribution for conversion of the water soluble oxygenated hydrocarbon reactant into the organic phase is at least 43%; and an aqueous phase; and then hydrogenating the organic phase, wherein ketones present in the organic phase are reduced to alcohols.
 7. The method of claim 6, further comprising converting the alcohols so formed to aromatic compounds.
 8. The method of any one of claims 1, 3, 4, or 6, wherein the catalyst comprises platinum, rhenium, or a combination of platinum and rhenium, disposed on a support selected from the group consisting of silica, alumina, zirconia, titania, ceria, vanadia, carbon, heteropolyacids, silica-alumina, silica nitride, boron nitride, and mixtures thereof.
 9. The method of claim 8, wherein the catalyst further comprises a reducible metal oxide selected from the group consisting of oxides of one or more of the following metals: Ti, V, Cr, Mn, Fe, Co, Nb, Mo, Sn, Sb, Te, W, Pb, Bi, Ce, and Eu.
 10. The method of claim 8, further comprising treating the support with an acid or a base, whereby surface chemistry of the support is modified to alter its acidic or basic properties.
 11. The method of claim 8, comprising reacting the aqueous solution at a temperature of from about 125° C. to about 727° C., at a pressure of from 14 psi to 725 psi. 